Chemicals and fuel blendstocks by a catalytic fast pyrolysis process

ABSTRACT

The present invention provides a catalytic fast pyrolysis process for the production of fuel blendstocks and chemicals. In addition, the invention provides compositions of renewable blendstocks, compositions of renewable fuel blends, and compositions of 100 percent renewable fuels compatible with gasoline specifications and regulations.

FIELD OF THE INVENTION

The present invention relates to an improved catalytic fast pyrolysisprocess. In particular, it relates to an improved process to producefuel blendstocks and chemicals from renewable feedstocks via catalyticfast pyrolysis, and to the chemicals, fuel blendstocks, and fuelcompositions produced thereby.

BACKGROUND OF THE INVENTION

A modern oil refinery converts crude oil through numerous unitoperations and conversion reactions into several individual streams,called including diesel, jet fuel, and gasoline blendstocks that arestored in separate tanks so they can be blended together in calculatedproportions to obtain various grades of “finished” gasoline thatconsumers purchase at the service station pump. The gasoline product isa complex blend of hydrocarbons that is subject to a variety oftechnical and regulatory limitations on the concentrations of certainindividual chemical compounds, chemical elements, and classes ofchemical components. Examples include limits on the amount of benzeneallowed in finished gasoline (currently 0.62% by volume), limits on theamount of organo-sulfur compounds which are limited indirectly by aspecification of the total amount of the element sulfur (currently 30ppm), and limits on the total amounts of aromatics and olefins, eitherdirectly for reformulated gasoline or indirectly through limitscalculated by the so-called “complex model” for air toxics asadministered by the US EPA. There are also physical property limits togasoline such as its Reid Vapor Pressure (RVP), and distillation mid andend points.

In the United States there are additional laws that require gasoline,jet, and diesel fuels to contain renewable-sourced blendstocks betweenspecific minimum and maximum levels. Today those limits are set byCongress via the Renewable Fuels Standards (“RFS”). The RFS mandatesthat 21 billion gallons of advanced biofuels will need to be produced by2022. A part of these advanced biofuels will be fungible transportationfuels such as gasoline, jet fuel, and diesel derived from biomass.Efforts continue on producing such fuels from biomass to meet themandate and it is perceived that there will be a strong demand forgasoline, jet, and diesel fuels produced economically from biomass. Thechief renewable-sourced gasoline blendstock used in the U.S. to meet thegasoline blending requirement is ethanol, produced largely from corn orsugar fermentation. A minor, but growing contribution to the nation'srenewable gasoline pool is so-called “second generation” cellulosicethanol made from non-food biomass such as corn stover.

There are several issues that make ethanol a less-desirable renewablegasoline blendstock. One of these is that most ethanol is produced fromcorn, which otherwise could be used for human or animal food.Furthermore, the land used to grow corn for ethanol production could bere-purposed to grow other kinds of food crops if other sources ofrenewable fuels besides ethanol could be produced. This is a societalissue that is a disadvantage for ethanol production; there are also manytechnical disadvantages of ethanol.

The technical disadvantages of ethanol as a fuel blendstock include thefact that ethanol is hygroscopic and therefore cannot be transported inpipelines that are used to ship conventional gasoline or other purehydrocarbon products, otherwise water drop-out and pipeline corrosionissues may occur. This has resulted in the establishment of a separateethanol supply chain and infrastructure, and the need for “splashblending” to make the final gasoline composition. Splash blending occurswhen ethanol is added to gasoline at the gasoline distribution andtanker truck depot which makes it more difficult for refineries tooptimize their intermediate “base” gasoline formulations (e.g.Reformulated Gasoline Blendstock for Oxygen Blending or “RBOB”, andConventional Blendstock for Oxygenate Blending or “CBOB”) that become“finished” gasoline after ethanol addition. This can result insub-optimal compositions that lead to “octane giveaway”, meaning thatconsumers might receive gasoline at a higher octane rating than what isstated on the service station pump label.

Further, ethanol has been shown to have a detrimental effect on certainelastomer sealing materials used in some gasoline engines and fuelsystems. This problem is worse for older engines and for non-roadengines such as those used for recreational vehicles such as boats andfour wheelers.

Another disadvantage of ethanol as a fuel blendstock is that ethanol haslower energy density than typical gasoline components because it is apolar molecule that contains the element oxygen. Compared to gasoline,ethanol has approximately 32% lower energy density per liquid volume ofproduct. The energy density of gasoline ranges from 112,000 to 116,000BTU/gal (44-46 MJ/kg), whereas ethanol is 76,000 BTU/gal (30 MJ/kg).

An important technical disadvantage of ethanol is its very high blendingReid Vapor Pressure (RVP). RVP is the absolute vapor pressure exerted bya material at 100° F. (37.8° C.). Blending RVP represents the material'scontribution to the RVP of a mixture such that the RVP for the mixtureequals the summation of each component's blend RVP multiplied by somefunction of that component's volume fraction. Although pure ethanol hasa relatively low RVP, the vapor pressures of ethanol-gasoline blends arehigher than expected from simple mixing due to non-ideal vapor-liquidsolution thermodynamics that occur because of the presence of thealcohol functional group. Ethanol has a blending RVP of more than 20 psiwhen blended at 10 volume percent in gasoline. It is important to notethat there is no single best volatility for gasoline. Volatility must beadjusted for the altitude and seasonal temperature of the location wherethe gasoline will be used. To meet strict RVP limits on finishedgasoline, especially for summertime blends, refiners reduce the vaporpressures of the base gasoline blends to low levels, prior to ethanolsplash blending. The lower vapor pressure limit forces refiners to “backout” relatively lower value materials such as butanes, pentanes, andother hydrocarbon components from gasoline, which creates additionalcosts.

Because of the fundamental limitation of ethanol-containing gasolineblend vapor pressure, the U.S. EPA has relaxed the finished gasoline RVPspecification for blends having 10% (volume) ethanol. These blends areallowed to have an RVP limit that is 1 psi higher than gasoline thatcontains no alcohol. The higher vapor pressure of the ethanol containinggasoline results in more evaporative emissions and resultant airpollution problems.

In the manufacture of ethanol by fermentation, various sources of sulfurare present including a relatively high level sulfur in the cornfeedstock (e.g. up to 1200 ppm in corn versus 500 ppm in pine andhardwoods), sulfur in the fermentation yeast, and the use of severalsulfur-containing acids to adjust pH, clean equipment, and removealdehydes from CO₂ (e.g. sulfuric acid, sulfamic acid, and sodiumbisulfite respectively). These contribute a relatively high level ofsulfur in ethanol blendstocks. Currently ASTM4806-15 is the standardregulating the specifications for fuel ethanol and it allows totalsulfur content up to 30 ppm, and sulfate is limited to 4 ppm maximum.Soon the limit on sulfur permitted in gasoline sold in the United Stateswill be reduced to 10 ppm maximum. The reduced sulfur limit will requirerefiners to reduce the sulfur content of their base gasolines further toaccommodate the high level of sulfur in the ethanol splash blend.

Biodiesel is a fuel having a fatty acid methyl ester (Fatty Acid MethylEster: FAME) component obtained by methyl esterification of fats andoils derived from living things by way of various methods. However, ifthe additive amount of biodiesel exceeds a certain value, the amount ofheat generation by the diesel engine will decrease, and it will not bepossible to heat the diesel particulate filter (DPF) to high temperatureand it will clog. In addition, the generation of injector deposits andcombustion deposits, causes deterioration of some fuel hoses resultingin unsafe vehicle operation. High concentrations of biodiesel can causesludge formation and oxidative degradation, which may induce clogging ofthe injectors, fuel filter, piping and the like, in addition toadversely affecting vehicle performance. As a result, use of biodieselrequires special allowances and frequent component replacement, and itsuse is limited to 5% by volume. Therefore, a renewable diesel fuelblendstock has been sought that can be blended in high concentrationsand used without special considerations.

For civilian or commercial aircraft, there are two main grades of jetfuel: Jet A-1 and Jet A. Jet fuels of both grades are kerosene-type fueland the difference between them is that Jet A-1 fulfills the freezingpoint requirement of maximum −47° C., whereas Jet A fulfills thefreezing point requirement of maximum −40° C. There is another grade ofjet fuel: Jet B for usage in a very cold climate, a wide-cut fuelcovering fractions from naphtha and kerosene, which fulfills thefreezing point requirement of maximum −50° C. Jet fuels generallycomprise at least 50% by weight hydrocarbon compounds with from 5 to 16carbon atoms.

Biomass pyrolysis has been developing as an alternative to ethanol forproviding renewable fuels and fuel blendstocks. The product of biomasspyrolysis is a complex and unstable bio oil whose composition varieswidely depending on feedstock and pyrolysis conditions, and thatcomprises hundreds of compounds including a plethora of oxygenates.Generally bio oil contains 20-40% by weight oxygen and a smallpercentage of sulfur-containing materials. Hydrotreatment of the biooil, including hydrodeoxygenation (HDO), hydrodesulfurization (HDS), andolefin hydrogenation, is required to make the oil suitable as ablendstock or stand-alone fuel. While hydrotreating is well developedfor petroleum feedstocks that contain almost no oxygen, the challengesof hydrotreating bio oil are more substantial. To date the preferredprocesses for hydrotreating bio oil are multi-stage systems that requirehigh pressure of hydrogen, precious metal catalysts, and multiple unitoperations (see for example, “Process Design and Economics for theConversion of Lignocellulosic Biomass to Hydrocarbon Fuels: FastPyrolysis and Hydrotreating Bio-oil Pathway,” S. Jones et al,PNNL-23053, November 2013, available electronically athttp://www.osti.gov/bridge).

Catalytic fast pyrolysis of biomass has been developed as an improvedthermal process for upgrading biomass to chemicals and fuels. Theprocess involves the conversion of biomass in a fluid bed reactor in thepresence of a catalyst. The catalyst is usually an acidic, microporouscrystalline material, usually a zeolite. The zeolite is active for theupgrading of the primary pyrolysis products of biomass decomposition,and converts them to aromatics, olefins, CO, CO2, char, coke, water, andother useful materials. The aromatics include benzene, toluene, xylenes,(collectively BTX), and naphthalene, among other aromatics. The olefinsinclude ethylene, propylene, and lesser amounts of higher molecularweight olefins. BTX aromatics are desirable products due to their highvalue and ease of transport. Toluene and xylenes are particularlydesirable as gasoline components due to their high octane rating andenergy density. Heavier aromatics are suitable precursors to jet anddiesel fuels. When produced under proper conditions, the products ofcatalytic fast pyrolysis are very low in oxygen content.

U.S. Pat. No. 9,062,264 discloses a process and system for producing arenewable gasoline by separating a bio-gasoline fraction from bio oil,and directly blending it with a petroleum-derived gasoline, without anyprior hydrotreatment. The disclosure also describes bio-gasolinecompositions derived from lignocellulosic biomass catalyticallypyrolyzed in a riser reactor in which the bio-gasoline containshydrocarbons and oxygenates wherein phenolic compounds comprise at least10% by weight, or carbon- and oxygen-containing compounds comprise atleast 15% by weight of the bio-gasoline.

U.S. Pat. Nos. 8,277,684 and 8,864,984 disclose that products from acatalytic fast pyrolysis process using zeolites such as HZSM-5 ascatalyst contain aromatics, that the products have high octane and canbe used directly as fuels or as fuel additives, and a method forproducing a biofuel or fuel additive composition with an octane numberof at least 90 from a solid hydrocarbonaceous biomass material. However,without further processing only very minute quantities of the rawproduct mixture can be blended into gasoline to produce a gasoline blendthat meets regulatory specifications. The disclosures do not address theconditions or processes required to produce a gasoline blendstock, theamount of fuel additive that could be used in a gasoline blending basestock or in a finished gasoline composition, or the properties of such ablended fuel. The disclosures do not suggest the removal of heteroatomcontaminants, such as sulfur, nitrogen, and oxygenates, how to achieve aproduct that meets the allowable limits of dienes, vinyl-aromatics (e.g.styrene), and olefins in the product, nor how to achieve variousgasoline blend specifications. The disclosures do not suggest conceptsor process configurations to produce C5/C6 naphtha, cyclohexane, linearalkyl benzenes, or naphthenes.

In U. S. Patent Publication No. 2014/0107306 A1, a method and apparatusare described for pyrolysis of biomass and conversion of at least onepyrolysis product to another chemical compound. The latter methodcomprises feeding a hydrocarbonaceous material to a reactor, pyrolyzingwithin the reactor at least a portion of the hydrocarbonaceous materialunder reaction conditions sufficient to produce one or more pyrolysisproducts, catalytically reacting at least a portion of the pyrolysisproducts, separating at least a portion of the hydrocarbon products, andreacting a portion of the hydrocarbon products to produce a chemicalintermediate.

In U.S. Pat. Nos. 8,277,643; 8,864,984; U.S. Patent Publication2012/0203042 A1; U. S. Patent Publication 2013/0060070 A1, U. S. PatentPublication 2014/0027265 A1; and US Patent Publication 2014/0303414 A1,each incorporated herein by reference in its entirety, apparatus andprocess conditions suitable for catalytic fast pyrolysis are described.

In light of current commercial practices and the disclosures of art, asimple economical process for producing renewable gasoline blendingstocks, diesel fuels, or jet fuels that meet technical and regulatorylimitations by use of catalytic pyrolysis of biomass is needed. Thepresent invention provides such a process and the resulting blendcompositions and chemicals.

SUMMARY OF THE INVENTION

Various aspects of the present invention include increased yield of fuelblendstocks and chemicals from renewable feedstocks via catalytic fastpyrolysis (CFP). The present invention provides for this in aneconomical improved process. An embodiment of the present processcomprises the steps of: a) feeding biomass, catalyst composition, suchas one comprising a crystalline molecular sieve characterized by asilica/alumina mole ratio (SAR) greater than 12 and a Constraint Index(CI) from 1 to 12, and transport fluid to a CFP process fluidized bedreactor maintained at reaction conditions to manufacture a raw fluidproduct stream, b) feeding the raw fluid product stream of step a) to asolids separation and stripping system to produce separated solids and afluid product stream, c) feeding the fluid product stream of step b) toa quench vapor/liquid separation system utilizing water or hydrocarbonquench to produce a liquid phase stream comprising water, char, coke,ash, catalyst fines, oxygenates, and C₉ ⁺ aromatics, and a vapor phasestream comprising carbon monoxide, carbon dioxide, hydrogen, olefins,and aromatics, said aromatics of the vapor phase stream selected fromthe group consisting of benzene, toluene, xylenes, phenols, naphthols,benzofuran, ethylbenzene, styrene, naphthalene, methylnaphthalene andcombinations thereof, d) feeding the vapor phase stream of step c) to acondensation system to produce an organic phase stream, e) feeding theorganic phase stream of step d) to a separation system to produce a highboiling fraction, such as one boiling at 185° C. and higher, and a lowboiling fraction, such as one boiling below 185° C., f) hydrotreating atleast a portion of the low boiling fraction of step e) at hydrotreatingconditions to produce a hydrotreated fraction, and g) recovering fuel,such as gasoline, blendstock comprising less than 0.4 weight % olefins,less than 10 ppm by weight sulfur, less than 10 ppm by weight nitrogen,and less than 1 weight % oxygen, from the hydrotreated fraction of stepf) in a product recovery system. Boiling ranges presented in thisinvention refer to the boiling ranges under modest pressure operation,typically 0.1 MPa, or from 0.05 to 1 MPa.

In another embodiment of the present invention, the blendstock recoveredin step g) further comprises at least 25, e.g. 25 to 60, volume %toluene, at least 15, e.g. 15 to 40, volume % benzene, at least 5, e.g.5 to 20, volume % xylenes, less than 15, e.g. 0.01 to <15, volume % C9+aromatics, and less than 10, e.g. 0.5 to <10, volume % paraffins, saidblendstock having a calculated octane rating ((R+M)/2) of at least 100,and a calculated RVP of less than 5 psia.

In another embodiment of the present invention, the blendstock recoveredin step g) further comprises at least 75, e.g. 75 to 99.9, volume %benzene, less than 20, e.g. 1 to <20, volume % total pentanes andhexanes, and less than 20, e.g. 1 to <20, volume % total toluene,xylenes, ethylbenzene and trimethylbenzenes, said blendstock having acalculated octane rating ((R+M)/2) of at least 99, and a calculated RVPof less than 7 psia.

In another embodiment of the present invention, the blendstock recoveredin step g) further comprises at least 50, e.g. 50 to 99, volume %toluene, less than 15, e.g. 0.1 to <15, volume % benzene, at least 10,e.g. 10 to 40, volume % xylenes, less than 15, e.g. 1 to <15, volume %C9+ aromatics, and less than 2, e.g. 0.01 to <2, volume % paraffins,said blendstock having a calculated octane rating ((R+M)/2) of at least100, and a calculated RVP of less than 3 psia.

In another embodiment of the present invention, the blendstock recoveredin step g) further comprises less than 1, e.g. 1 ppm to <1, volume %benzene, less than 10, e.g. 1 to <10, volume % total pentanes andhexanes, less than 1, e.g. 1 ppm to <1, weight % total of the sum oftoluene, xylenes, trimethylbenzenes and naphthalene, and at least 80,e.g. 80 to 99, volume % cyclohexane, said blendstock having a calculatedoctane rating ((R+M)/2) of at least 75, and a calculated RVP of lessthan 7 psia.

In another embodiment of the present invention the blendstock recoveredin step g) further comprises less than 1 volume % benzene, less than 10volume % total pentanes and hexanes, less than 1 weight % toluene, lessthan 1 weight % xylenes, less than 1 weight % trimethylbenzenes andnaphthalene, and at least 80 volume % cyclohexanes comprisingcyclohexane, and methyl-, dimethyl-, ethyl-, methyl-ethyl- orpropyl-alkylated cyclohexanes, said blendstock having a calculatedoctane rating ((R+M)/2) of at least 70, and a calculated RVP of lessthan 7 psia.

In another embodiment of the present invention the blendstock recoveredin step g) further comprises 50 to 99 volume % the sum of cyclohexane,methyl-cyclohexane, dimethyl-cyclohexane, ethyl-cyclohexane,methyl-ethyl-cyclohexane, and propyl-cyclohexanes, less than 15 volume %benzene, from 0.01 to 2 volume % paraffins, less than 0.4 weight %olefins, less than 10 ppm by weight sulfur, less than 10 ppm by weightnitrogen, and less than 1 weight % oxygen, said blendstock having acalculated octane rating ((R+M)/2) of at least 70, and a calculated RVPof less than 7 psia. This cyclohexanes-rich blendstock may be mixed withgasoline, or ethanol, or diesel, or jet fuel to produce renewable fuelmixtures. Another embodiment of the invention comprises a mixture offrom 90 to 99.9 volume % gasoline and from 0.1 to 10 volume % of thecyclohexanes-rich blendstock. Another embodiment of the inventioncomprises a mixture of from 50 to 99 volume % ethanol and from 50 to 1volume % of the cyclohexanes-rich blendstock. Another embodiment of theinvention comprises a mixture of from 50 to 99 volume % diesel fuel andfrom 50 to 1 volume % of the cyclohexanes-rich blendstock. Anotherembodiment of the invention comprises a mixture of from 50 to 99 volume% jet fuel and from 50 to 1 volume % of the cyclohexanes-richblendstock.

In another embodiment of the present invention, the blendstock recoveredin step g) further comprises at least 30, e.g. 30 to 60, volume %toluene, less than 10, e.g. 1 to <10, volume % benzene, at least 5, e.g.5 to 25, volume % xylenes, less than 5, e.g. 0.1 to <5, volume % totalpentanes and hexanes, less than 10, e.g. 1 to <10, volume % totaltrimethylbenzenes and naphthalene, and at least 10, e.g. 10 to 40,volume % cyclohexane, said blendstock having a calculated octane rating((R+M)/2) of at least 95, and a calculated RVP of less than 5 psia.

In another embodiment of the present process, step e) compriseshydrotreating the organic phase stream of step d) at hydrotreatingconditions to produce a hydrotreated stream, and step f) comprisesfeeding the hydrotreated stream of step e) to a separation system toproduce a hydrotreated high boiling fraction, such as one boiling at185° C. and higher, and a hydrotreated low boiling fraction, such as oneboiling below 185° C., and step g) comprises recovering fuel blendstockcomprising less than 0.4 weight % olefins, less than 10 ppm by weightsulfur, less than 10 ppm by weight nitrogen, and less than 1 weight %oxygen from the hydrotreated low boiling fraction of step f).

Another embodiment of the present process comprises the steps of: i)feeding biomass, catalyst composition, such as one comprising acrystalline molecular sieve characterized by an SAR greater than 12 anda CI from 1 to 12, and transport fluid to a CFP process fluidized bedreactor maintained at reaction conditions to manufacture a raw fluidproduct stream, ii) feeding the raw fluid product stream of step i) to asolids separation and stripping system to produce separated solids and afluid product stream, iii) feeding the fluid product stream of step ii)to a quench vapor/liquid separation system utilizing water orhydrocarbon quench to produce a liquid phase stream comprising water,char, coke, ash, catalyst fines, oxygenates, and C9+ aromatics, and avapor phase stream comprising carbon monoxide, carbon dioxide, hydrogen,olefins, and aromatics, said aromatics of the vapor phase streamselected from the group consisting of benzene, toluene, xylenes,phenols, naphthols, benzofuran, ethylbenzene, styrene, naphthalene,methylnaphthalene and combinations thereof, iv) feeding the vapor phasestream of step iii) to a condensation system to produce an organic phasestream, v) feeding the organic phase stream of step iv) to a separationsystem to produce a high boiling fraction, such as one boiling at 185°C. and higher, and a low boiling fraction, such as one boiling below185° C., vi) feeding the low boiling fraction of step v) to a separationsystem to produce a fraction boiling above 85° C. and a fraction boilingbelow 85° C., vii) alkylating at least a portion of the fraction boilingbelow 85° C. of step vi) by contact with an alkylating agent atalkylating conditions to produce an alkylated fraction, or hydrogenatingat least a portion of the fraction boiling below 85° C. of step vi) athydrogenating conditions to produce a hydrogenated fraction, or both,and viii) recovering chemicals comprising ethylbenzene, cumene,propylbenzenes, linear alkylbenzenes wherein the alkyl chain comprisesfrom 10 to 16 carbon atoms, or a combination thereof, from the alkylatedfraction of step vii), or chemicals comprising cyclohexane from thehydrogenated fraction of step vii), or both, in a product recoverysystem.

Another embodiment of the present invention comprises such processwherein the crystalline molecular sieve of the catalyst of step a) or i)has a structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35,ZSM-38, ZSM-48, ZSM-50 or combinations thereof.

In another embodiment of the invention, step vi) comprises feeding thelow boiling fraction of step v) to a separation system to produce afraction boiling above 78° C. and a fraction boiling below 78° C., stepvii) comprises alkylating at least a portion of the fraction boilingbelow 78° C. of step vi) by contact with an alkylating agent atalkylating conditions to produce an alkylated fraction, or hydrogenatingand at least a portion of the fraction boiling below 78° C. of step vi)at hydrogenating conditions to produce a hydrogenated fraction, or both,and step viii) comprises recovering chemicals comprising ethylbenzene,cumene, propylbenzenes, linear alkylbenzenes wherein the alkyl chaincomprises from 10 to 16 carbon atoms from the alkylated fraction of stepvi), or chemicals comprising cyclohexane from the hydrogenated fractionof step vi), or both, in a product recovery system.

Another embodiment comprises a fuel blendstock comprising from 25 to 60volume % toluene, from 15 to 40 volume % benzene, from 5 to 20 volume %xylenes, from 0.01 to 15 volume % C₉ ⁺ aromatics, from 0.5 to 10 volume% paraffins, less than 0.4 weight % olefins, less than 10 ppm by weightsulfur, less than 10 ppm by weight nitrogen, and less than 1 weight %oxygen, said blendstock having a calculated octane rating ((R+M)/2) ofat least 100, and a calculated RVP of less than 5 psia.

Another embodiment comprises a fuel blendstock comprising from 75 to99.9 volume % benzene, from 1 to 20 volume % total pentanes and hexanes,from 1 to 20 volume % total toluene, xylenes, ethylbenzene andtrimethylbenzenes, less than 0.4 weight % olefins, less than 10 ppm byweight sulfur, less than 10 ppm by weight nitrogen, and less than 1weight % oxygen, said blendstock having a calculated octane rating((R+M)/2) of at least 99, and a calculated RVP of less than 7 psia.

Another embodiment comprises a fuel blendstock comprising from 50 to 99volume % toluene, 10 to 40 volume % xylenes, from 0.1 to 15 volume %benzene, from 1 to 15 volume % C₉ ⁺ aromatics, from 0.01 to 2 volume %paraffins, less than 0.4 weight % olefins, less than 10 ppm by weightsulfur, less than 10 ppm by weight nitrogen, and less than 1 weight %oxygen, said blendstock having a calculated octane rating ((R+M)/2) ofat least 100, and a calculated RVP of less than 3 psia.

Another embodiment comprises a fuel blendstock comprising from 1 ppm to1 weight % benzene, from 1 to 10 volume % total pentanes and hexanes,from 1 ppm to 1% by weight total toluene, xylenes, trimethylbenzenes andnaphthalene, from 80 to 99 volume % cyclohexane, less than 0.4 weight %olefins, less than 10 ppm by weight sulfur, less than 10 ppm by weightnitrogen, and less than 1 weight % oxygen, said blendstock or chemicalstock having a calculated octane rating ((R+M)/2) of at least 75, and acalculated RVP of less than 7 psia.

Another embodiment comprises a fuel blendstock comprising from 30 to 60volume % toluene, from 1 to 10 volume % benzene, from 5 to 25 volume %xylenes, from 0.1 to 5 volume % total pentanes and hexanes, from 1 to 10volume % total trimethylbenzenes and naphthalene, from 10 to 40 volume %cyclohexane, less than 0.4 weight % olefins, less than 10 ppm by weightsulfur, less than 10 ppm by weight nitrogen, and less than 1 weight %oxygen, said blendstock having a calculated octane rating ((R+M)/2) ofat least 95, and a calculated RVP of less than 5 psia.

In another embodiment of the present process, step e) comprises feedingthe organic phase stream of step d) to a separation system to produce ahigh boiling fraction, such as one boiling at 185° C. and higher, and alow boiling fraction, such as one boiling below 185° C., step f)comprises hydrogenating at least a portion of the fraction boiling above185° C. of step e) at hydrogenating conditions to produce a hydrogenatedfraction, and step g) comprises recovering fuel blendstock componentsfrom the hydrogenated fraction of step f). The fuel blendstock preparedin this embodiment may comprise decalin, substituted decalins, e.g.methyl decalin, tetralin, substituted tetralins, e.g. methyl tetralin,and other bicyclic paraffin or aromatic materials. The fuel blendstockprepared in this embodiment may comprise hydrocarbons with from 5 to 16carbon atoms, or hydrocarbons with at least 9 carbon atoms, or both.

In another embodiment of the invention the hydrogen gas that is utilizedfor the hydrotreatment or hydrogenation in step f), or step e), or stepg), or in any other step, or in multiple steps, is separated from theproduct gas stream or generated from the product gas stream in a watergas shift reaction, partial oxidation, or gasification of a heavierproduct fraction, or both separated and generated within the process.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1, 2, 3 and 4 are block flow illustrations of embodiments of thepresent process.

FIGS. 5, 6 and 7 are block flow illustrations of various unit operationsof the present process.

DETAILED DESCRIPTION OF THE INVENTION

As a result of extensive research in view of the above, we have foundthat we can economically and effectively conduct a CFP process toenhance manufacture of valuable fuel blendstock and chemical products byway of a series of sequential steps.

An embodiment of the present improved process comprises steps of: a)feeding biomass, such as, for example, that provided from renewablesources of organic materials, catalyst composition, such as comprisingone or more crystalline molecular sieves, for example, thosecharacterized by a SAR greater than 12 and a Constraint Index from 1 to12, and transport fluid to a CFP process fluidized bed reactormaintained at reaction conditions, for example, a temperature from 300to 1000° C. and pressure from 0.1 to 1.5 MPa, to manufacture a raw fluidproduct stream, b) feeding the raw fluid product stream of step a) to asolids separation and stripping system, hereinafter more particularlydescribed, to produce separated solids and a fluid product stream, c)feeding the fluid product stream of step b) to a water or hydrocarbonquench vapor/liquid separation system, hereinafter more particularlydescribed, to produce a liquid phase stream comprising components suchas those selected from the group consisting of water, char, coke, ash,catalyst fines, oxygenates, and C₉ ⁺ aromatics, and combinationsthereof, and a vapor phase stream comprising carbon monoxide, carbondioxide, hydrogen, olefins, and aromatics, said aromatics of the vaporphase stream selected from the group consisting of benzene, toluene,xylenes, phenols, naphthols, benzofuran, ethylbenzene, styrene,naphthalene, methylnaphthalene and combinations thereof, d) feeding thevapor phase stream of step c) to a condensation system, hereinafter moreparticularly described, to produce an organic phase stream, e) feedingthe organic phase stream of step d) to a separation system to produce ahigh boiling fraction, such as one boiling at 185° C. and higher, and alow boiling fraction, such as one boiling below 185° C., f)hydrotreating at least a portion of the low boiling fraction, or aportion of the high boiling fraction, or both, of step e) athydrotreating conditions to produce a hydrotreated fraction orfractions, and g) recovering fuel blendstock, such as gasolineblendstock, or diesel, or jet fuel, comprising less than 0.4 weight %olefins, less than 10 ppm by weight sulfur, less than 10 ppm by weightnitrogen, and less than 1 weight % oxygen, from the hydrotreatedfraction of step f) in a product recovery system.

Embodiments of the invention include the novel fuel blendstocksrecovered by step g) and mixtures thereof with fuels, such as gasoline,jet fuel, diesel fuel, or other fuel blendstocks, such as ethanol.

In one embodiment of the invention the fuel blendstock comprises atleast 50, or at least 75, or at least 90, or from 50 to 99, or from 75to 95% by weight hydrocarbons with from 5 to 16 carbon atoms. Anotherembodiment of the invention comprises the mixture of the aboveblendstock with petroleum derived materials in a jet fuel product.Another embodiment of the invention comprises a mixture of thisrenewable mixture with petroleum-derived materials such as jet fuelwherein the renewable mixture comprises from 0.1 to 50 volume % and jetfuel comprises from 50 to 99.9 volume % of the mixture.

In one embodiment of the invention the fuel blendstock comprises atleast 50, or at least 75, or at least 90, or from 50 to 99, or from 75to 95% by weight hydrocarbons with 9 or more carbon atoms. Anotherembodiment of the invention comprises the mixture of the aboveblendstock with petroleum-derived materials in a diesel fuel product.Another embodiment of the invention comprises a mixture of thisrenewable mixture with petroleum-derived materials such as diesel fuelwherein the renewable mixture comprises from 0.1 to 50 volume % anddiesel fuel comprises from 50 to 99.9 volume % of the mixture.

An embodiment of the present improved process comprises steps of: i)feeding biomass, such as, for example, that provided from renewablesources of organic materials, catalyst composition, such as comprisingone or more crystalline molecular sieves, for example, thosecharacterized by a SAR greater than 12 and a CI from 1 to 12, andtransport fluid to a CFP process fluidized bed reactor maintainedreaction conditions, for example, a temperature from 300 to 1000° C. andpressure from 0.1 to 1.5 MPa, to manufacture a raw fluid product stream,ii) feeding the raw fluid product stream of step i) to a solidsseparation and stripping system, hereinafter more particularlydescribed, to produce separated solids and a fluid product stream, iii)feeding the fluid product stream of step ii) to a quench vapor/liquidseparation system, hereinafter more particularly described, utilizingwater or hydrocarbon quench to produce a liquid phase stream comprisingwater, char, coke, ash, catalyst fines, oxygenates, and C₉ ⁺ aromatics,and a vapor phase stream comprising carbon monoxide, carbon dioxide,hydrogen, olefins, and aromatics, said aromatics of the vapor phasestream selected from the group consisting of benzene, toluene, xylenes,phenols, naphthols, benzofuran, ethylbenzene, styrene, naphthalene,methylnaphthalene and combinations thereof, iv) feeding the vapor phasestream of step iii) to a condensation system, hereinafter moreparticularly described, to produce an organic phase stream, v) feedingthe organic phase stream of step iv) to a separation system, hereinaftermore particularly described, to produce a high boiling fraction, such asone boiling at 185° C. and higher, and a low boiling fraction, such asone boiling below 185° C., vi) feeding the low boiling fraction of stepv) to a separation system, hereinafter more particularly described, toproduce a fraction boiling above 85° C. and a fraction boiling below 85°C., vii) alkylating at least a portion of the fraction boiling below 85°C. of step vi) by contact with an alkylating agent at alkylatingconditions to produce an alkylated fraction, or hydrogenating at least aportion of the fraction boiling below 85° C. of step vi) athydrogenating conditions to produce a hydrogenated fraction, or both,and viii) recovering chemicals comprising ethylbenzene, cumene,propylbenzenes, linear alkylbenzenes wherein the alkyl chain comprisesfrom 10 to 16 carbon atoms, or a combination thereof, from the alkylatedfraction of step vii), or chemicals comprising cyclohexane from thehydrogenated fraction of step vii), or both, in a product recoverysystem.

As used herein, the terms “aromatics” or “aromatic compound” refer to ahydrocarbon compound or compounds comprising one or more aromatic groupssuch as, for example, single aromatic ring systems (e.g., benzyl,phenyl, etc.) and fused polycyclic aromatic ring systems (e.g.,naphthyl, 1,2,3,4-tetrahydronaphthyl, etc.). Examples of aromaticcompounds include, but are not limited to, benzene, toluene, indane,indene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, trimethylbenzene(e.g., 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene,1,2,3-trimethylbenzene, etc.), ethylbenzene, styrene, cumene,n-propylbenzene, xylenes (e.g., p-xylene, m-xylene, o-xylene),naphthalene, methylnaphthalene (e.g., 1-methylnaphthalene), anthracene,9,10-dimethylanthracene, pyrene, phenanthrene, dimethyl naphthalene(e.g., 1,5-dimethylnaphthalene, 1,6-dimethylnaphthalene,2,5-dimethylnaphthalene, etc.), ethyl naphthalene, hydrindene,methylhydrindene, and dimethylhydrindene. Single ring and/or higher ringaromatics may also be produced in some embodiments. Aromatics alsoinclude single and multiple ring compounds that contain heteroatomsubstituents, i.e., phenol, cresol, benzofuran, aniline, indole, etc.

As used herein, the term “biomass” has its conventional meaning in theart and refers to any organic source of energy or chemicals that isrenewable. Its major components can be: (1) trees (wood) and all othervegetation; (2) agricultural products and wastes (corn stover, fruit,garbage ensilage, etc.); (3) algae and other marine plants; (4)metabolic wastes (manure, sewage), and (5) cellulosic urban wasteExamples of biomass materials are described, for example, in Huber, G.W. et al, “Synthesis of Transportation Fuels from Biomass: Chemistry,Catalysts, and Engineering,” Chem. Rev. 106, (2006), pp. 4044-4098.

Biomass is conventionally defined as the living or recently deadbiological material that can be converted for use as fuel or forindustrial production. The criterion as biomass is that the materialshould be recently participating in the carbon cycle so that the releaseof carbon in the combustion process results in no net increase averagedover a reasonably short period of time (for this reason, fossil fuelssuch as peat, lignite and coal are not considered biomass by thisdefinition as they contain carbon that has not participated in thecarbon cycle for a long time so that their combustion results in a netincrease in atmospheric carbon dioxide). Most commonly, biomass refersto plant matter grown for use as biofuel, but it also includes plant oranimal matter used for production of fibers, chemicals or heat. Biomassmay also include biodegradable wastes or byproducts that can be burnedas fuel or converted to chemicals, including municipal wastes, greenwaste (the biodegradable waste comprised of garden or park waste, suchas grass or flower cuttings and hedge trimmings), byproducts of farmingincluding animal manures, food processing wastes, sewage sludge, andblack liquor from wood pulp or algae. Biomass excludes organic materialwhich has been transformed by geological processes into substances suchas coal, oil shale or petroleum. Biomass is widely and typically grownfrom plants, including miscanthus, spurge, sunflower, switchgrass, hemp,corn (maize), poplar, willow, sugarcane, and oil palm (palm oil) withthe roots, stems, leaves, seed husks and fruits all being potentiallyuseful. Processing of the raw material for introduction to theprocessing unit may vary according to the needs of the unit and the formof the biomass. Biomass can be distinguished from fossil-derived carbonby the presence of 14C in amounts significantly above that found infossil fuels.

Biomass used in the present process can most preferably be solidmaterials chosen from among wood, forestry waste, corn stover, andcombinations thereof.

As used herein, the terms “olefin” or “olefin compound” (a.k.a.“alkenes”) have their ordinary meaning in the art, and refer to anyunsaturated hydrocarbon containing one or more pairs of carbon atomslinked by a double bond. Olefins include both cyclic and acyclic(aliphatic) olefins, in which the double bond is located between carbonatoms forming part of a cyclic (closed ring) or of an open chaingrouping, respectively. In addition, olefins may include any suitablenumber of double bonds (e.g., monoolefins, diolefins, triolefins, etc.).Examples of olefin compounds include, but are not limited to, ethene,propene, allene (propadiene), 1-butene, 2-butene, isobutene(2-methylpropene), butadiene, and isoprene, among others. Examples ofcyclic olefins include cyclopentene, cyclohexene, and cycloheptene,among others. Aromatic compounds such as toluene are not consideredolefins; however, olefins that include aromatic moieties are consideredolefins, for example, benzyl acrylate or styrene.

As used herein, the term “oxygenate” includes any organic compound thatcontains at least one atom of oxygen in its structure such as alcohols(e.g., methanol, ethanol, etc.), acids (e.g., acetic acid, propionicacid, etc.), aldehydes (e.g., formaldehyde, acetaldehyde, etc), esters(e.g., methyl acetate, ethyl acetate, etc.), ethers (e.g., dimethylether, diethyl ether, etc.), aromatics with oxygen containingsubstituents (e.g., phenol, cresol, benzoic acid etc.), cyclic ethers,acids, aldehydes, and esters (e.g. furan, furfural, etc.), and the like.

As used herein, the terms “pyrolysis” and “pyrolyzing” have theirconventional meaning in the art and refer to the transformation of acompound, e.g., a solid hydrocarbonaceous material, into one or moreother substances, e.g., volatile organic compounds, gases and coke, byheat, preferably without the addition of, or in the absence of,molecular oxygen, i.e. O₂. Preferably, the volume fraction of oxygenpresent in a pyrolysis reaction chamber is 0.5% or less. Pyrolysis maytake place with or without the use of a catalyst. “Catalytic pyrolysis”refers to pyrolysis performed in the presence of a catalyst, and mayinvolve steps as described in more detail below. Catalytic fastpyrolysis that involves the conversion of biomass in a catalytic fluidbed reactor to produce a mixture of aromatics, olefins, and a variety ofother materials is a particularly beneficial pyrolysis process. Examplesof catalytic pyrolysis processes are outlined, for example, in Huber, G.W. et al, “Synthesis of Transportation Fuels from Biomass: Chemistry,Catalysts, and Engineering,” Chem. Rev. 106, (2006), pp. 4044-4098,incorporated herein by reference.

As used herein, the term “recovery” of a component is the fraction (orpercent) of that component that is present in the recovered productstream(s) compared to the amount of that component that is present inthe reactor effluent stream. For example if 10 grams of “A” is presentin the reactor effluent and 8.5 grams of “A” is present in the recoveredproduct stream, then the recovery of “A” is 8.5/10 or 0.85 (85%). Allpercentages provided herein are by mass unless otherwise indicated.

Catalyst components useful in the context of this invention can beselected from any catalyst known in the art, or as would be understoodby those skilled in the art. Catalysts promote and/or effect reactions.Thus, as used herein, catalysts lower the activation energy (increasethe rate) of a chemical process, and/or improve the distribution ofproducts or intermediates in a chemical reaction (for example, a shapeselective catalyst). Examples of reactions that can be catalyzedinclude: dehydration, dehydrogenation, isomerization, oligomerization,cracking, hydrogen transfer, aromatization, decarbonylation,decarboxylation, aldol condensation, molecular cracking anddecomposition, combinations thereof, and other reactions. Catalystcomponents can be considered acidic, neutral or basic, as would beunderstood by those skilled in the art.

For catalytic fast pyrolysis, useful catalysts include those containinginternal porosity selected according to pore size (e.g., mesoporous andpore sizes typically associated with zeolites), e.g., average pore sizesof less than 100 Angstroms (Å), less than 50 Å, less than 20 Å, lessthan 10 Å, less than 5 Å, or smaller. In some embodiments, catalystswith average pore sizes of from 5 Å to 100 Å may be used. In someembodiments, catalysts with average pore sizes of between 5.0 Å and 6.5Å, or between 5.9 Å and 6.3 Å may be used. In some cases, catalysts withaverage pore sizes of between 7 Angstroms and 8 Å, or between 7.2 Å and7.8 Å may be used.

The catalyst composition particularly advantageous in the CFP fluidizedbed reactor of the present invention comprises a crystalline molecularsieve characterized by an SAR greater than 12 and a CI from 1 to 12.Non-limiting examples of these crystalline molecular sieves are thosehaving the structure of ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35,ZSM-48, ZSM-50 or combinations thereof. As an embodiment, the catalystcomposition comprises a crystalline molecular sieve characterized by anSAR from greater than 12 to 240 and a CI from 5 to 10, such as, forexample, molecular sieves having the structure of ZSM-5, ZSM-11, ZSM-22,ZSM-23 or combinations thereof. The method by which CI is determined isdescribed more fully in U.S. Pat. No. 4,029,716, incorporated byreference for details of the method.

The molecular sieve for use herein or the catalyst compositioncomprising same may be thermally treated at high temperatures. Thisthermal treatment is generally performed by heating at a temperature ofat least 370° C. for a least 1 minute and generally not longer than 20hours (typically in an oxygen containing atmosphere, preferably air).While subatmospheric pressure can be employed for the thermal treatment,atmospheric pressure is desired for reasons of convenience. The thermaltreatment can be performed at a temperature up to about 925° C. Thethermally treated product is particularly useful in the present process.

For the catalyst composition useful in this invention, the suitablemolecular sieve may be employed in combination with a support or bindermaterial such as, for example, a porous inorganic oxide support or aclay binder. Non-limiting examples of such binder materials includealumina, zirconia, silica, magnesia, thoria, titania, boria andcombinations thereof, generally in the form of dried inorganic oxidegels and gelatinous precipitates. Suitable clay materials include, byway of example, bentonite, kieselguhr and combinations thereof. Therelative proportion of suitable crystalline molecular sieve of the totalcatalyst composition may vary widely with the molecular sieve contentranging from 30 to 90 percent by weight and more usually in the range of40 to 70 percent by weight of the composition. The catalyst compositionmay be in the form of an extrudate, beads or fluidizable microspheres.

The molecular sieve for use herein or the catalyst compositioncomprising it may have original cations replaced, in accordance withtechniques well known in the art, at least in part, by ion exchange withhydrogen or hydrogen precursor cations and/or non-noble metal ions ofGroup VIII of the Periodic Table, i.e. nickel, iron and/or cobalt.

In embodiments that require hydrogen for hydrotreatment orhydrogenation, the required hydrogen can be separated from the productgases or generated from the product gases via the water gas shiftreaction (WGSR), or from partial oxidation of product gases, or fromgasification of one of several heavier product fractions.CO+H₂O→H₂+CO₂  (1)

The key reaction of the WGSR process is depicted in equation (1). In theWGSR at least a portion of the carbon monoxide reacts with water toshift the equilibrium to produce hydrogen and carbon dioxide. The WGSRis an equilibrium limited reaction, and the formation of hydrogen isfavored at lower temperatures. The reaction is generally conducted overa catalyst; there are high temperature (HT) catalysts, low temperature(LT) catalysts, and sulfur tolerant catalysts. Typical high temperatureWGSR catalysts include iron-based catalysts such as zinc ferrite(ZnFe₂O₄), ferric oxide (Fe₂O₃), magnetite (Fe₃O₄), chromium oxides, andmixtures such as iron/chromia (90-95% Fe₂O₃ and 5-10% Cr₂O₃). The hightemperature shift is usually conducted at 300-450° C. and pressures from0.1 to 10 MPa (1 to 100 bar), although high pressure is not required.The pressure is usually dictated by the other unit operations in theprocess or the pressure at which the hydrogen is to be utilized. Theshift catalysts employed at lower temperatures include copper promotedzinc oxide, copper promoted chromia, other catalysts with coppersupported on metal oxides, and mixtures thereof. The LT WGSR process isconducted at 200-275° C. and 0.1 to 10 MPa. Low temperature shiftcatalysts are poisoned by sulfur and chlorine compounds, so often aguard bed of ZnO or other sulfur or halogen scavenger is used to removetraces of these impurities. For this reason sulfur tolerant WGSRcatalysts based on Mo and Co have been developed for sulfur containingfeeds. The water gas shift reaction is a highly exothermic equilibriumreaction and requires active control of the reactor temperature toproduce the desired products.

In this invention, the gaseous product stream remaining after condensingthe organic fraction in step d) or iv) comprises CO, CO₂, H₂, CH₄, lightolefins, and traces of other materials. In order to produce hydrogen bythe WGSR for use in the hydrotreatment or hydrogenation steps, the COcan be separated from the other components, although depending on theconcentrations of these it may not be necessary. A typical product gasstream may comprise 30 to 60 volume % CO, 20 to 45% CO₂, 3 to 10% CH₄, 2to 7% ethylene plus propylene, 0.2 to 5% hydrogen, and traces of othermaterials. Carbon dioxide inhibits the WGSR, so it can be removed in anamine scrubber or trapped with CaO or other absorbent. Olefins can beremoved by hydrogenation to paraffins. After preliminary purificationthe CO stream can be mixed with steam and passed over a HT catalyst, aLT catalyst, or a series of HT and then LT catalysts to producehydrogen. Lower temperatures favor hydrogen production so the typicalexit temperature from the WGSR system is 180 to 220° C. for the LTprocess. The hydrogen produced from the WGSR process can be used in thehydrotreatment or hydrogenation processes of the invention.

Another route to produce hydrogen for the hydrotreatment orhydrogenation processes of the invention is the partial oxidation of thelight hydrocarbons in the gaseous product stream from step d). Inparticular, the methane can be partially oxidized with molecular oxygento produce a gaseous product comprising approximately a 2:1 mixture ofhydrogen and carbon monoxide, although the gas mixture may be oxidizedwithout separation or purification. The H₂ content of the mixture of H₂and CO obtained from partial oxidation may be further increased in aWGSR step, or the product gas may be used for hydrotreatment orhydrogenation provided the activity of the chosen catalyst is notpoisoned or inhibited by the presence of CO.

Yet another embodiment of the invention that utilizes hydrogen generatedfrom byproducts of the catalytic fast pyrolysis for the hydrotreating orhydrogenation steps comprises the gasification of one or more of avariety of heavier product fractions. Gasification is well known in theart and it is practiced worldwide with application to solids and heavyliquid fossil fuels, including refinery bottoms. The gasificationprocess of the invention uses partial oxidation to convert carbonaceousmaterials, such as C₉ ⁺ products, oxygenates, char, coke, biofuel, orbiomass with oxygen at high temperature, i.e., greater than 800° C.,into synthesis gas (mixture of hydrogen and carbon monoxide), steam, andelectricity. The synthesis gas comprising carbon monoxide and hydrogencan be enriched in hydrogen via the WGSR discussed previously, orutilized directly in a hydrotreating or hydrogenation process providedthe catalyst is not sensitive to CO poisoning or inhibition.

In another embodiment of the invention, hydrogen recovered from withinthe inventive process such as by WGSR of CO, partial oxidation ofhydrocarbons, or gasification of heavy materials, is utilized tohydrocrack one of the various heavy oxygenate, heavy aromatic, e.g. C₉⁺, or the materials boiling above 185° C. recovered from steps e) or f)or elsewhere. In this embodiment the hydrocracked products may in partbe returned to the catalytic pyrolysis reactor in step a) or may in partbe combined with one of the fuel blendstocks.

Several embodiments of the invention are depicted in FIGS. 1, 2, 3, and4, wherein process 100 is the Bio-TCat™ process. Examples of apparatusand process conditions suitable for the Bio-TCat™ process 100 aredescribed in U.S. Pat. Nos. 8,277,643, 8,864,984, and 9,169,442, andUnited States Patent Publications 2014/0027265 A1, 2014/0303414 A1 and2013/0060070 A1, each incorporated herein by reference. Conditions forBio-TCat™ conversion of biomass may include one or a combination of thefollowing features (which are not intended to limit the broader aspectsof the invention): biomass treatment, a catalyst composition; thatcatalyst composition optionally comprising a metal; a fluidized bed,circulating bed, moving bed, or riser reactor; a fluidizing fluid; anoperating temperature in the range of 300 to 1000° C. and a pressure inthe range of 0.1 to 3.0 MPa (1 to 30 atm); and a solid catalyst/biomassmass ratio of from 0.1 and 40. Solid biomass may be fed to the reactorin a continuous or intermittent fashion. Solid catalyst may beregenerated in an oxidative process and in part returned to the reactor.Solid catalyst may be removed from the reactor, stripped with steam todisplace organic materials and reactive gases, and then regenerated in afluid bed catalyst regenerator by treatment with an oxygen containinggas, and in part returned to the reactor. To reduce the fraction ofnon-aromatic components in the products, and thereby benefit downstreamseparation and conversion technologies, the reaction severity in theBio-TCat™ reactor can be increased. Methods to achieve greater reactionseverity include higher reaction temperature, higher catalyst activitywhich can be achieved by higher fresh catalyst makeup and spent catalystremoval rates, or by changes to the catalyst (e.g. higher zeolitecontent, lower silica/alumina ratio, greater macro and meso-porosity,etc), higher pressure, or longer residence time.

Biomass may not be available in a convenient form for processing in thefluid bed reactor of the Bio-TCat™ process. While solid biomass is thepreferred feed, the solid biomass may comprise portions of liquids atambient conditions. Solid biomass may be treated in any of a number ofways to make it more suitable for processing including cutting,chopping, chipping, shredding, pulverizing, grinding, sizing, drying,roasting, torrefying, washing, extracting, or some combination of thesein any order to achieve the desired properties of the biomass feed as tosize, moisture, sulfur and nitrogen impurities content, density, andmetals content. Procedures to inhibit biomass clumping and agglomerationmay be employed.

Following conversion in the fluid bed reactor, the products of Bio-TCat™process 100 are recovered by a combination of solids separation, wateror hydrocarbon quenching, gas-liquid separation, compression cooling,gas-liquid absorption, condensation of condensable compounds, or othermethods known in the art, to produce a mixture of C₄ ⁺ hydrocarbonsincluding species having boiling points above those of gasoline oron-road diesel fuels. Distillation can be used to separate out thedesirable C₅-C₉ cut. This product can them be subject to mildhydrotreatment to remove heteroatoms and reduce the dienes,vinyl-aromatics, and olefins present as contaminants, and provide afirst liquid stream. Alternatively a Bio-TCat™ product having a broaderboiling range than C₅-C₉ (e.g. C₄-C₁₂ or higher) can be hydrotreatedfirst prior to distillation to recover the C₅-C₉ fraction.

The C₅-C₉ aromatics-rich liquid product that is produced by thecatalytic pyrolysis of biomass material over a zeolite catalyst iscalled “AnelloMate”. The aromatic concentration in AnelloMate isextremely high compared to current petroleum-based processes that makearomatics, such as naphtha reforming and steam cracker pyrolysisgasolines. This is believed to be a consequence of the reactionchemistry, the high reaction severity, and the selectivity that thecatalytic fast pyrolysis catalyst has for aromatics at the expense ofnon-aromatic species such as paraffins, olefins, and dienes. The highconcentration of aromatics is advantageous in subsequent, downstreamseparation and conversion processes.

After recovery and separation from solids, by-product water, lightgases, and heavy C₁₀ ⁺ hydrocarbons and oxygenates, the AnelloMatenaphtha-range product is subject to mild hydrotreating to remove therelatively low levels of organo-sulfur and organo-nitrogen compounds,and oxygenates that are co-produced in trace amounts by the pyrolysisprocess. The mild hydrotreating step reduces the amount ofheteroatom-containing hydrocarbons in the product to less than 1 ppmeach. Mild hydrotreating may also hydrogenate undesirable dienes,vinyl-aromatics, and olefins to their saturated analogs, but thesaturation of aromatic rings is avoided to prevent unnecessary hydrogenconsumption and loss of gasoline octane rating that occurs when aromaticrings are saturated to their corresponding naphthenic rings. Thehydrotreatment may be conducted by contacting the liquid with ahydrogen-containing gas at a pressure from 0.1 MPa to 40 MPa (1 to 400atm), preferably 0.2 to 2 MPa (2 to 20 atm), at a temperature from 40 to350° C., preferably from 40 to 250° C., liquid hourly space velocity of0.1 to 19 hr-1, preferably 1 to 4 hr-1, gas to liquid ratio of 1 to 25m3/m3, preferably 5 to 20 m3/m3, in the presence of a solid catalyst.The hydrogen-containing gas may comprise at least 90%, or at least 95%,or at least 98% H₂. Solid catalysts useful for the hydrotreating processstep include Ni, Co, Fe, Cu, Zn, Ag, Pt, Pd, Ru, Rh, Ir, Mo, W, orcombinations thereof, deposited on oxide supports including oxides ofAl, Si, Ti, Zr, Th, Mg, Ca, or some combination of these, either ascrystalline solids or as amorphous mixtures. In some cases the catalystmay comprise chlorinated alumina, a zeolite, active carbon, clays,aluminous cements, rare earth oxides, or alkaline-earth oxides. Thehydrotreatment can be carried out in a fixed bed, trickle bed, catalyticdistillation reactor, or fluid bed reactor, with counter- or co-currentflow of feed and H₂. To control the exothermic heat of reaction, reactorvessels may be designed to contain several separate beds of catalysthaving liquid and gas distributors or re-distributors between them.Under these conditions the majority of heteroatom compounds areconverted to hydrocarbons and the heteroatoms are rejected as H₂S, NH₃,or water. Suitable conditions and operation of distillation reactors aredescribed in U.S. Pat. No. 8,808,533, and United States PatentPublication 2010/0063334, incorporated herein by reference. Productsfrom the hydrotreating reactor are cooled to 40° C. and the pressure isreduced to 2.3 MPa (23 atm) before being discharged into a high pressureseparator flash drum. In the drum, the hydrogen-rich gas is separatedfrom the liquid product. Hydrogen-containing off-gas from the separatoris sent to the recycle gas compressor which is used to circulatehydrogen back to the reactor. A slip stream containing excess hydrogenand the light gas products from the hydrotreating reactions is removed,and is either re-processed to remove the contaminants in it (e.g. water,H₂S, NH₃, etc) or used downstream in the benzene saturation reactor. Theliquid product from the high pressure separator contains some dissolvedlight gases that are removed downstream in the main fractionator.

The hydrotreated products are separated into a heavy C₁₀ ⁺ fraction anda C₅-C₉ fraction in a packed or trayed tower that operates at about 0.36MPa (3.6 atm) pressure, contains about 25 theoretical stages, anoverhead condenser operating at about 40° C., and a bottom reboileroperating at about 264° C. Feed is pre-heated in the main fractionatorfeed heater to 150° C. and fed to the column on an intermediate tray.The overhead recycle ratio can be 2.5 by mass. The distillate productcontains the full-range C₅-C₉ AnelloMate product, and the bottomsproduct contains a C₁₀ ⁺ heavy fraction. A small amount of waste gas isgenerated and removed from the overhead condenser accumulation drum.

In some embodiments, a C₆ splitter is introduced into the processing ofthe hydrotreated Bio-TCat™ product to improve product separation andrecovery and permit production of useful fuel blendstocks and chemicals.By introducing a C₆ splitter into the process, the majority of benzenecan be separated and processed by a variety of means including: benzenesaturation with hydrogen, as shown in FIG. 1, benzene alkylation withlow molecular weight olefins, either produced by the Bio-TCat™ processor fed from a separate source, as shown in FIG. 2, benzene conversion tolinear alkyl benzenes by alkylation with C₁₀-C₁₆ alpha-olefins, as shownin FIG. 3, or benzene recovery as a high purity stream that can be usedfor various processes, as shown in FIG. 4.

As shown in FIG. 1, hydrotreated full-range AnelloMate C₅-C₉ productstream 2 can be separated by distillation or other means into a secondliquid distillate stream 4 that comprises C₅-C₆ naphtha, benzene, andother low boiling components, and a third liquid bottoms stream 5 thatcomprises C₇ ⁺ materials including toluene, xylenes, trimethylbenzenes,and other higher boiling components but which has a very low benzeneconcentration. The amount of benzene in the third liquid stream 5comprising C₇ ⁺ materials can be controlled by the design of thedistillation tower, such as by the number of trays or height of packingmaterial used in the tower to effect separation, or by distillationtower operation, or both. Similarly the amount of toluene in the secondliquid stream 4 comprising C₅-C₆ naphtha can be controlled in the samemanner Preferably the distillation of stream 2 into two fractions can beconducted so that materials with normal boiling points below about 85°C. are collected overhead and those materials with normal boiling pointsabove about 85° C. are collected in the column bottoms. The refluxratio, which is the amount of overhead material returned to the columndivided by the amount of overhead product withdrawn from the tower, isan operating parameter that can be used to control the concentration ofbenzene in the bottom product. The naphtha distillate product stream 4can comprise at least 85, or at least 90, or at least 94, or from 85 to99.9, or from 90 to 99% benzene by weight. The naphtha distillateproduct stream 4 can have a toluene concentration less than 5%, or lessthan 2%, or less than 1%, or less than 0.5, or less than 0.2, or from0.01 to 5, or from 0.01 to 1% by weight. The C₇ ⁺ bottom product stream5 can have a benzene concentration less than 5, or less than 2, or lessthan 1, or less than 0.5, or less than 0.2, or from 0.01 to 5, or from0.01 to 1% by weight. The C₇ ⁺ stream 5 can be further separated into atoluene stream comprising at least 90%, or at least 95%, or at least99.5% toluene, or a xylenes stream comprising at least 90%, or at least95%, or at least 99.5% xylenes by weight, or both.

As depicted in FIG. 1, after separation of the C₇ ⁺ materials, thestream 4 is optionally routed to a benzene saturation reactor where thebenzene in the stream is saturated by hydrogen in the presence of acatalyst and converted with near 100% selectivity to cyclohexane in astream 6. The composition of stream 6 can be at least 85%, or at least90%, or at least 95%, or at least 99% cyclohexane. The benzene-depletedlight naphtha of stream 6 can then be blended into gasoline, oroptionally used as a feedstock in a cyclohexane conversion process suchas for oxidation to cyclohexanol, cyclohexanone, or both, which is astep in the upgrading sequence leading to Nylon manufacture. Onecommercial benzene saturation process 120 that could be used to treatthe Bio-TCat™ light naphtha 4 is the BenFree™ process licensed by Axens.Stream 5 comprising toluene and xylenes can be used in a blend stock orcan optionally be sent to an aromatics separation process 130, as shownin FIG. 1, to produce purified chemical feedstocks. A portion of thebenzene-depleted light naphtha of stream 6 can be combined with aportion of stream 5 that comprises toluene and xylenes in any proportionthat comprises at least 1% by volume of the benzene-depleted stream andat least 1% by volume of the toluene-containing stream to form agasoline blendstock.

Alternatively, the benzene-rich light naphtha stream 4 can be used asfeedstock in a benzene conversion and functionalization step to makeuseful chemicals, or benzene can be converted or removed to provide afuel blendstock having lower benzene content. FIG. 2 presents aconceptual block flow diagram of a process of the invention forproducing gasoline blendstocks and chemicals that includes thealkylation of benzene with light olefins. As shown in FIG. 2, afterseparation the benzene-rich light naphtha stream 4 can be alkylated witheither ethylene, propylene, or a mixture of C₂-C₄ olefins in thepresence of an alkylation catalyst in a benzene alkylation unit 140 tomake ethylbenzene, propylbenzenes (e.g. 1-, or 2-propylbenzene), orboth, which can be blended into gasoline, stream 9, or optionallyupgraded to a variety of chemicals stream 8. Ethylbenzene orpropylbenzene streams of at least 85% or at least 90%, or at least 95%by weight ethylbenzene or propylbenzenes or both can be obtained byfurther separation by distillation or other conventional separationprocesses. Optionally, the ethylbenzene can be upgraded bydehydrogenation to styrene, and polymerization of the styrene to makepolymers. Optionally, cumene can be separated from the alkylated benzenestream and provided to an oxidation process to prepare phenol andacetone. The olefins used for the alkylation can be olefins recoveredfrom the products of the Bio-TCat™ process. Any C₅-C₇ non-aromaticspresent in the original naphtha can also be blended into gasoline, andthus no pre- or post-purification of the alkylated product is needed fora fuels application. Stream 5 comprising toluene and xylenes can be usedin a blend stock or can optionally be sent to an aromatics separationprocess 130, as shown in FIG. 2.

FIG. 3 presents a conceptual block flow diagram of an embodiment of theinvention for producing gasoline blendstocks and chemicals that includesthe alkylation of benzene with C10-C16 linear alpha olefins to producelinear alkyl benzenes (LABs). LABs are intermediates in the productionof surfactants for use in detergents, particularly biodegradabledetergents. As shown in FIG. 3, after separation the benzene-rich lightnaphtha stream 4 can be alkylated with a mixture of C₁₀-C₁₆ alphaolefins in a benzene alkylation unit 140 to make linear alkyl-benzeneswhich can be separated into a light C₅/C₆ material to be blended intogasoline, stream 11, and a mixture of LABs, stream 10. The mixture ofLABs can comprise a mixture wherein at least 75%, or at least 85%, or atleast 95%, or at least 99% of the linear alkyl benzenes comprisematerials with molecular weight from 218 to 302 grams per mole.Optionally, the LABs stream 10, or some fraction thereof, can besulfonated with SO3 or its equivalent to produce linear alkylbenzenesulfonates. Any C₅-C₇ non-aromatics present in the original naphtha canalso be blended into gasoline, and thus no pre- or post-purification ofthe alkylated product is needed for a fuels application. Stream 5comprising toluene and xylenes can be used in a blendstock or canoptionally be sent to an aromatics separation process 130, as shown inFIG. 3.

FIG. 4 presents a conceptual block flow diagram of an embodiment of theinvention for producing gasoline blendstocks and chemicals that includesthe separation of light naphtha low boiling materials and dissolvedgases from the lightly hydrotreated C₅-C₉ products, stream 1, of theBio-TCat™ process 100. In FIG. 4 a stabilizer column 150(“de-hexanizer”) is placed before the C₆ splitter 110. The de-hexanizercolumn removes some of the lighter C₁-C₆ paraffins, stream 12, in theBio-TCat™ C₅-C₉ product, prior to separation of the benzene. Separationof the higher boiling stream 13 in the de-hexanizer 150 results in ahigher purity benzene stream 14 from the C₆ splitter 110 overhead. Thede-hexanizer 150 is designed to separate compounds with normal boilingpoints below 75° C. into the overhead stream 12, and recover compoundswith normal boiling points above 75° C. in stream 13. As shown in FIG.4, the benzene-rich stream 14 can be removed by distillation to providea low benzene naphtha stream 5 and a high purity benzene stream 14 thatcan be upgraded in unit 160 operation by hydrogenation to cyclohexane 16or by an alkylation process (not shown) as presented in FIG. 2 or 3.

Another option to produce additional renewable blending materials thatmay be favored when renewable materials command a premium value, is tohydrogenate a portion of the mixed aromatic stream, either streams 1, 3,or 5 in FIGS. 1, 2, 3, and 4. The hydrogenation of the mixed aromaticscan be performed in a manner similar to the hydrotreatment describedabove, except the conditions for saturating aromatics are generally moresevere than for hydrogenating olefins. The temperature of the aromaticshydrogenation may be between 300 and 450° C., pressures of 1.5 to 5.5MPa (15 to 55 bar gauge), liquid hourly space velocities of 0.5 to 5hr-1, hydrogen partial pressures of 0.5 to 3.0 MPa (5 to 30 bar), andtotal hydrogen circulation rates of 25 to 350 nm³ of H₂ per m³ of feed.Catalyst can be of the conventional types used for naphtha pre-treatingprocesses with petroleum fractions (e.g. cobalt/molybdenum on alumina,nickel/molybdenum on alumina, nickel/tungsten, etc). Recovery of theproducts of the hydrogenation of the mixed aromatics may produce aproduct mixture consisting of compounds chosen from among thecyclohexanes including cyclohexane, and methyl-, dimethyl-, ethyl,methyl-ethyl- or propyl-alkylated cyclohexanes, or other multiplyalkylated cyclohexanes.

Downstream recovery and purification of the reactor effluent was modeledusing the Aspen Plus™ process simulation software package. FIGS. 5-7show process flow diagrams for the process. These process flow diagramsrepresent preliminary optimizations for minimal capital and operatingcosts, and for other common engineering practices such as heat andenergy integration. Using conventional engineering practices, oneskilled in the art could accomplish further cost and energy optimizationbased on the designs presented herein.

As shown in FIG. 5, hot reaction product vapors at 3.2 barg pressure(0.42 MPa absolute pressure) exit the Bio T-Cat™ reactor and may becooled from 575° C. to 475° C. in a heat exchanger (not shown in FIG.5). The cooling can be facilitated by steam generation on the cold sideof the exchanger. The hot product from the exchanger is sent to a waterquench tower 200 where the vapors are cooled to about 75° C., optionallyusing water that is produced by the Bio-TCat™ process. The quench towerin the model contains four theoretical trays, although this can beoptimized to provide the desired separation. Most of the hydrocarbonsexit with the quench tower overhead vapors. The overhead vapors arecompressed in compressor 201 to over 8 bar gauge (0.9 MPa) and cooled to5° C. in a heat exchanger 202 and chiller 203. Various types ofcommercially available industrial chilling units can be used toaccomplish this. At this temperature and pressure, a substantial amountof C5-C12 hydrocarbons are condensed along with some water. Thehydrocarbon and water separate into a hydrocarbon-rich upper layer and awater-rich lower layer in the 3-phase separation drum 210. Thehydrocarbon-rich liquid product is sent downstream to the BTXNcollection drum 220 prior to hydrotreating for removal of sulfur,nitrogen, and oxygen impurities.

There is still recoverable hydrocarbon in the off-gas stream exiting the3-phase separator. This stream is contacted with heavy diesel oil (e.g.“lean oil”) in a gas-liquid absorber tower (e.g. “lean oil absorber”)230. Hydrocarbons in the vapor phase are transferred to the liquid, anda negligible amount of diesel is lost to the vapor phase. The oilexiting the bottom of the absorber contains much of the hydrocarbon thatentered as vapor, and thus this oil is referred to as “rich oil”. Theabsorber column 230 is either a packed or trayed contactor modeled with7 theoretical trays and operating at 7 barg (0.8 MPa). The top tray ofthe absorber operates at about 35° C., due to the hot incoming lean oil,but the lower sections of the tower are cooler due to the large amountof low temperature product gas passing through the tower. Conventionalpetroleum-sourced diesel, or renewable bio-diesel, or a by-productstream of the process can be used as the oil.

Light hydrocarbons in the rich oil are recovered in a rich oil stripper240. This is a 20 theoretical stage packed or trayed tower with areboiler 242 and overhead condenser 241. The tower 240 operates at about2 barg (0.3 MPa) pressure, and rich oil feed enters the tower at stage5. A recycle ratio of 2:1 by mass is used to control the overheadtemperature of the column to about 130° C. The overhead condenser 241return temperature is 40° C. and the reboiler 242 temperature is 329° C.The overhead liquid distillate product is rich in BTX hydrocarbons.These are also sent to the BTXN collection drum 220. The bottoms productfrom the rich oil stripper is substantially free of BTXN components. Itis cooled to 100° C. and recycled to the lean oil absorber 230 in acontinuous process or is optionally in part sent to a separatecollection drum (not shown). An absorber and rich oil stripperfeed-effluent heat exchanger 243 and a lean oil cooler 244 are used toadjust the temperature of the lean oil being fed to the absorber.

The quench tower bottoms product exits the tower around 115° C. and 3.3bar gauge (0.43 MPa) pressure. This liquid product is cooled to 40° C.and sent to a phase separation drum 250. Any hydrocarbons that form alight upper liquid phase are removed and sent to the BTXN collectiondrum 220 or to a separate product collection drum. A large amount ofcooled water is recycled back to the top of the quench tower where it isused to remove the heat contained in the Bio-TCat™ reactor effluent.Alternatively, the product recovery section could be designed to usesome of the BTXN product as a liquid quench medium for the quench towerinstead of water. In this case, the predominant liquid exiting the phaseseparation drum would be hydrocarbon, and the water product and moisturewould be removed as a lower liquid phase.

FIG. 6 is a process flow diagram for the hydrotreating reactor (HDT) andthe main fractionator. The HDT reactor uses hydrogen to convertheteroatom containing organic compounds to their correspondinghydrocarbon products. The main fractionator is used to separate out C₄to C₉ or C₅ to C₉ hydrocarbon product from heavy C₁₀ ⁺ products such asindane, indene, naphthalene, and other multi-ring compounds.

The collected BTXN product described in FIG. 5 is pumped to 25.5 bargauge (2.6 MPa) by the feed pump 301. Makeup hydrogen at 98% purity(remainder is carbon monoxide) is used as fresh hydrogen makeup to theHDT reactor. A compressor 302 is used to elevate the hydrogen pressureto match reaction conditions. The untreated liquid BTXN product isheated in a feed-effluent exchanger 303 and then a heater 304 to come totypical hydrotreating temperatures (see below). The heater can use anysuitable method including exchange with a hotter fluid, or in a firedheater that uses a fuel such as natural gas or one of the high-BTU wastegases generated by the Bio-TCat™ process or its downstream recoverysections.

In the hydrotreating reactor 300, trace levels of organo-sulfur,nitrogen, and oxygen compounds are removed by reaction with hydrogen.Conditions in the reactor are temperatures between 300 and 350° C.,pressures of 15 to 55 bar gauge (1.6 to 5.6 MPa), liquid hourly spacevelocities of 0.5 to 5 hr-1, hydrogen partial pressures of 5 to 30 bar(0.5 to 3.0 MPa), and total hydrogen circulation rates of 25 to 350 nm3of H₂ per m3 of liquid feed. Catalyst can be of the conventional typesused for naphtha pre-treating processes with petroleum fractions (e.g.cobalt/molybdenum on alumina, nickel/molybdenum on alumina,nickel/tungsten, etc). Under these conditions the majority of heteroatomcompounds are converted to hydrocarbons and the heteroatoms are rejectedas H₂S, NH₃, or water. To control the exothermic heat of reaction,reactors vessels may be designed to contain several separate beds ofcatalyst having liquid and gas distributors or re-distributors betweenthem. The reactor beds may be operated in a 3-phase ‘trickle bed’ modewhereby there are liquid and vapor reactants in contact with the solidcatalyst, or in 2-phase mode where all reactants are in the vapor phase.

Products from the hydrotreating reactor are cooled in product cooler 306to 40° C. and the pressure is reduced to 22 bar gauge (2.3 MPa) beforebeing discharged into a high pressure separator flash drum 310. In thedrum, the hydrogen-rich gas is separated from the liquid product.Hydrogen-containing off-gas from the separator is sent to the recyclegas compressor 305 which is used to circulate hydrogen back to thereactor. A slip stream containing excess hydrogen and the light gasproducts from the hydrotreating reactions is removed and is eitherre-processed to remove the contaminants in it (e.g. water, H₂S, NH₃,etc) or used downstream in the benzene saturation reactor. The liquidproduct from the high pressure separator contains some dissolved lightgases that will be removed downstream in the main fractionator.

The main fractionator in the model, 320, is a packed or trayed towerthat operates at about 2.6 bar gauge (0.36 MPa) pressure, contains 25theoretical stages, an overhead condenser 321 operating at 40° C., and abottom reboiler 322 operating at about 264° C. Feed is pre-heated in themain fractionator feed heater to 150° C. and fed to the column on abouttray 18. The overhead recycle ratio is 2.5 by mass. The distillateproduct contains the “full-range C5-C9 AnelloMate product,” and thebottoms product contains a C₁₀ ⁺ heavy fraction. A small amount of wastegas is generated and removed from the overhead condenser accumulationdrum 323.

The full-range hydrotreated AnelloMate product is suitable as feed to aconventional petroleum refinery aromatics plant, or to a separation andupgrading plant solely dedicated to processing renewable aromatics. Theproduct is also acceptable as a gasoline blendstock.

To reduce benzene content for fuels, or to provide a benzene-richchemicals feedstock, the full-range product can be separated furtherinto a C₆ ⁻ fraction and a C₇ ⁺ fraction using a C₆ splitter tower. FIG.7 shows the process flow for a C₆ splitter, followed by a benzenesaturation unit.

The C₆ splitter is a trayed or packed column 400 operating at about 0.8bar gauge (0.18 MPa), that contains 50 theoretical stages, an overheadcondenser 401 operating at 40° C., and a reboiler 402 temperature ofabout 140° C. The reflux ratio varies between 2 and 3. A C₆ ⁻ product isobtained overhead and the C₇ ⁺ heavy naphtha is obtained from thebottom. The design and operation of the fractionator may be optimized tominimize the amount of toluene or heavier aromatics in the C₆ ⁻ overheadproduct, and minimize the amount of benzene in the C₇ ⁺ heavy naphthaproduct.

Minimization of toluene in the overhead product is necessary to reducethe loss of toluene by hydrogenation to methyl-cyclohexane in thebenzene saturation unit, or reduce the production of methyl-ethyl- ormethyl-propyl-benzenes by alkylation with ethylene or propylene, orreduce the production of methyl-long alkyl chain benzenes in linearalkyl-benzene alkylation, or reduce the amount of hydrogen consumptiondue to reaction with toluene, or to reduce the octane loss when tolueneis converted to methyl cyclohexane by hydrogenation, or several of thesereasons. Similarly, high concentrations of benzene in the C₇ and heavierproduct limit the quantity of that product that can be blended intogasoline due to strict limits on benzene content.

The C₆ ⁻ stream can be used as feed stock for a benzene conversionprocess such as alkylation with ethylene and/or propylene to makeethylbenzene or propylbenzene, alkylated with long-chain alpha olefinsto make linear alkyl-benzene, or the benzene can be hydrogenated to makecyclohexane. FIG. 7 shows the benzene saturation unit. The benzenesaturation reactor 410 uses high pressure hydrogen to convert benzene tocyclohexane. The flow sequence and process design is very similar tothat used for hydrotreating the full-range product from the Bio-TCat™reactor. Common catalysts for the conversion of benzene to cyclohexaneinclude nickel on alumina or platinum on alumina. Operating pressuresare 20-30 bar gauge (2.1-3.1 MPa). Temperature control is very importantto avoid thermal runaway reactions due to the large exothermic heatrelease, and to promote the high conversion of benzene which is favoredat lower temperatures. Typical temperatures around 150-205° C. arepreferred. Various reactor types can be used to convert benzene tocyclohexane including trickle beds or multi-tubular reactors.

The cyclohexane product from the benzene saturation reactor is cooled to40° C., and the hydrogen is flashed off at 22 bar pressure (2.3 MPa) inseparator drum 420. The high pressure liquid is then sent to a flashdrum 430 operating at near atmospheric pressure. Additional light gas isflashed off at these conditions. The resulting cyclohexane-rich productcan be used as a solvent, as a feedstock for making nylon precursors(e.g. cyclohexanol and cyclohexanone), or used as a source of renewablegasoline blend stock.

Table 1 is a summary of the product purities obtained in the simulation.One item to note is that the recovered yields of certain products fromthe Bio-TCat™ process are more than what actually exited from thereactor. The increase in yields and the high recovery values are due tocertain conversion processes that occurred in the hydrotreating step.For example, phenol can be converted to benzene, and cresols can beconverted to toluene by hydrogenation and removal of the alcohol groupfrom the ring. This increases the yield of desirable aromatic product.It also serves to reduce the boiling point of the mixture, for examplephenol boils at 181° C. but benzene boils at 80° C. Similarly cresolsboil in the 190-205° C. range, but toluene boils at 111° C.

TABLE 1 (Composition of Bio-TCat ™ Streams) Stream 2 Volume Full- Stream4 Stream 6 Stream 5 Heavy Percent Range C6 Minus Cyclohexane C7 PlusAromatics Benzene 34.4% 94.8% 0.0% 0.5% 0.0% Toluene 44.9% 0.0% 1.3%70.3% 0.0% Xylenes 13.8% 0.0% 0.1% 21.7% 0.0% EB 0.7% 0.0% 0.0% 1.2%0.0% Styrene 0.5% 0.0% 0.0% 0.8% 0.0% C9's 2.0% 0.0% 0.0% 3.2% 0.0% C4+1.5% 3.8% 97.7% 0.2% 0.3% Non- Aromatics C5+ 1.2% 3.0% 97.2% 0.2% 0.3%Non- Aromatics Heavies 1.4% 0.0% 0.0% 2.2% 100.0% Light C3 0.6% 1.4%0.8% 0.0% 0.0% Minus Totals 99.9% 100.0% 100.0% 99.9% 100.3%

In some embodiments a benzene-rich fraction is upgraded in a primaryproduct upgrading process comprising the catalytic alkylation of benzenewith ethylene to produce ethylbenzene or the catalytic alkylation ofbenzene with propylene to produce cumene and propylbenzene, or thecatalytic alkylation of benzene with C₁₀-C₁₆ terminal olefins to produceLABs, or some combination of these. In practicing some embodiments ofthis invention, a portion of the effluent of the alkylation reactionzone is reintroduced into the alkylation reaction zone to enhance theyield of useful products via transalkylation. In embodiments thatinclude the alkylation of benzene by ethylene or propylene, the ratio ofthe weight of the olefin entering the alkylation catalyst bed in theolefinic feed stream per unit time to the sum of the weights ofcompounds entering the alkylation catalyst bed per the same unit time,multiplied by 100, is generally less than 1.88, preferably less than1.3, and more preferably less than 0.01. This ratio is sometimesreferred to herein as the olefin ratio. When the alkylation of benzeneincludes reaction with C₁₀-C₁₆ olefins the weight ratio of olefin tobenzene can be from 0.1 to 5, or the mole ratio of olefin to benzene canbe from 0.01 to 1. The alkylation conditions may comprise a maximumolefin concentration based on the weight of compounds entering thealkylation catalyst bed of preferably less than 1.88 wt %, mostpreferably less than 1.3 wt %, and still more preferably less than 0.01wt %.

The aromatic feed stream and the olefinic feed stream are preferablycombined upstream of the alkylation catalyst bed. The alkylationreaction zone can comprise one or more alkylation catalyst beds and/orone or more alkylation catalyst reactors, and each reactor may containone or more alkylation catalyst beds.

Alkylation conditions for this process include a molar ratio of phenylgroups per alkyl group of typically from 1:1 to about 25:1. In someembodiments, the molar ratio may be less than 1:1, and may be down to0.75:1 or lower. Preferably, the molar ratio of phenyl groups per ethylgroup (or propyl group, in cumene production) is below 6:1, and in someembodiments, in the range of 2:1 to 4:1.

In general, for a given molar ratio of alkylation substrate peralkylation agent, especially an olefinic alkylation agent, the greaterthe molar ratio of phenyl groups to alkyl groups in the feed stream, theless is the rise in temperature in the reaction zone that occurs as aresult of the alkylation reactions. Although the reactor may haveindirect heat exchange means to remove the heat as it is produced, thereactor is preferably adiabatic, and so the outlet temperature of theeffluent stream is higher than the inlet temperature of the reactants.The appropriate reaction temperature may be preferably from 100° C. tothe critical temperature of the alkylation substrate, which may be 475°C. or even higher, the inlet temperature in the reaction zone isgenerally from 200 to 260° C., and preferably from 230 to 250° C. Thetemperature rise is typically from 5 to 50° C., and preferably less than20° C. The temperature rise in the reaction zone may be controlled byadjusting the molar ratio of phenyl groups to ethyl groups in the feedstream, for example by recycling portions of the reactor effluent.Recycling reactor effluent to the reaction zone of the alkylationreactor does not interfere in a significant way with the extent of thealkylation or transalkylation reactions, and recycling reactor effluentmay be employed for the purpose of controlling reaction zonetemperatures.

Alkylation is preferably performed in the liquid phase. Consequently,reaction pressure needs to be sufficiently high to ensure at least apartial liquid phase. Where ethylene is the alkylating agent olefin, thepressure range for the reactions is usually from about 200 to about 1000psi(g) (1.4 to 7.0 MPa(g)), more commonly from about 300 to about 600psi(g) (2.0 to 4.1 MPa(g)), and even more commonly from about 450 toabout 600 psi(g) (3.1 to 4.1 MPa(g)). Preferably, the reactionconditions are sufficient to maintain benzene in a liquid phase and aresupercritical conditions for ethylene. For olefins other than ethylene,this invention may be practiced generally at a pressure of from 50 to1000 psi(g) (3.4 to 7.0 MPa(g)).

The weight hourly space velocity (WHSV) of alkylating agent ethylenepreferably ranges from 0.01 to 2.0 hr⁻¹, whereas for C₁₀-C₁₆ olefins theWHSV is from 001 to 20 hr⁻¹. The WHSV of aromatics, including benzeneand a polyalkylaromatic having at least two C₂ ⁺ groups, if any,preferably ranges from 0.3 to 500 hr⁻¹.

Volatility is the property of a liquid fuel that defines its evaporationcharacteristics. RVP is an abbreviation for “Reid Vapor Pressure,” acommon measure of and generic term for gasoline volatility. RVP is ameasure of the volatility of the blend, based on measurements using ASTMD-323, or subsequent ASTM methods including D-5191 and D-4814. RVP isusually expressed in units of psi because RVP is measured directly fromthe pressure gauge, and reported without addition of atmosphericpressure, although the units are sometimes designated as psia. RVP canbe estimated by calculation by entering chemical composition data intocommercially available software (e.g. Aspen™ process simulation) tocalculate the RVP of the mixture. Alternatively for complex blends (e.g.“mix”) where the RVP of individual streams or molecular components areknown, either by measurement or by calculation, and it is desired toestimate the RVP of the resulting blend, the RVP Index method developedby Chevron Inc (Fundamentals of Petroleum Refining, by Mohamed A. Fahim,Taher A. Al-Sahhaf, Amal Elkilani, Elsevier 2010) can be used. In thismethod, the RVP values for each individual blend stock or molecularcomponent is raised to the 1.25 exponent, added together using eachstream's respective blending volume contribution to the pool, and thentaking the 1.25 root of the sum. This is shown below in Equation (2).(RVP_(mix))^(1.25)=(Σ(RVP_(i) ^(1.25) *v _(i)))/(Σv _(i))  (2)

In equation (2), v_(i) is the volume fraction of each stream making upthe final gasoline blend, and RVP_(i) is the blending RVP of eachstream. RVP_(mix) is the RVP of the resulting final blend.

In the U. S., the EPA has established regulations for the vapor pressureof gasoline sold at retail stations to reduce evaporative gasolineemissions that contribute to ground-level ozone and to diminish theeffects of ozone-related health problems. Depending on the state andmonth, gasoline RVP may not exceed 9.0 psi or 7.8 psi. EPA provides a1.0 psi RVP allowance, i.e. 1.0 psi higher RVP, for gasoline containingethanol at 9 to 10 volume percent, meaning that gasoline blendscontaining this amount of ethanol may be sold at 10.0 or 8.8 psi.

In addition to the volatility requirements set forth in ASTM 4814,gasolines typically must meet a minimum octane posted at the pump,typically (R+M)/2 of 87 octane for regular grade gasoline and 91 to 93octane for a premium grade gasoline. In many regions, refiners may offera mid-grade gasoline having octane and additive packages placing thequality of the gasoline somewhere between regular and premium grades. Atypical octane for a mid-grade gasoline is about 89.

Octane number is a measure of the knocking tendency of fuels inspark-ignited gasoline engines. Knock refers to prematurethermo-chemical induced combustion ignition that occurs in the enginecylinder before the electric spark occurs. It is undesired because ofpotential damage to engine components. The higher the octane rating of afuel, the less prone it is to knock in the engine. High octane fuels canalso sustain higher cylinder compression which provides increased poweroutput per engine weight (e.g. specific power) to those engines designedfor high compression ratio operation.

Based on the chemical compositions, the octane number of a mixture canbe estimated with reasonable accuracy using existing blending models.Octanes can be calculated using the octane number blending model ofJaffe et al (Ind. Eng. Chem. Res. 2006, 45, 337-345). Table 2 presentsthe octane number, the octane blending coefficient “β” (see Jaffe etal), and RVP of the compounds used in the calculations. No interactionparameters as described by Jaffe et al (e.g. k₁₂) were used here.

TABLE 2 (Physical Property Data for Individual Components used tocalculate the Physical Properties of Products Streams) Compound Densityg/cm3 RON MON β_(RON) β_(MON) i-pentane 0.6244 92.0 90.3 2.0204 0.4278n-pentane 0.6311 62.0 62.6 2.0559 0.3092 hexanes & hexenes 0.6579 76.073.9 2.0204 0.4278 benzene 0.8846 102.7 105.0 3.3984 0.4773 cyclohexane0.7834 82.5 77.2 1.6870 0.2821 heptanes & heptenes 0.6881 90.0 78.02.0559 0.3092 methyl cyclohexane 0.7740 82.0 77.0 1.6870 0.2821 toluene0.8717 118.0 103.5 3.3984 0.4773 octanes & octenes 0.7068 90.0 77.02.0559 0.3092 ethyl benzene 0.8717 112.0 105.0 3.3984 0.4773 o-xylene0.8847 112.0 105.0 3.3984 0.4773 m-xylene 0.8689 112.0 105.0 3.39840.4773 p-xylene 0.8657 112.0 105.0 3.3984 0.4773 nonane & nonenes 0.721950.0 60.0 2.0559 0.3092 C9 aromatics 0.8664 110.0 101.0 3.3984 0.4773C10+ aromatics 0.9650 105.0 94.0 3.3984 0.4773

An object of this invention is to provide valuable gasoline blendstockcompositions, chemical feedstocks, or both, through the biomassupgrading processes depicted in FIGS. 1 through 7. Aromatic productfractions, produced by catalytic pyrolysis of biomass, separation ofcondensable materials from the raw product, mild hydrotreatment, andseparation of a fraction that has a boiling point below about 185° C.,and further separation of this fraction into a lighter fraction withboiling point below about 85° C., and a heavier fraction with boilingrange about 85 to about 185° C. are contemplated.

One embodiment of the present invention is a renewable fuel, e.g.gasoline, processing feedstock that comprises a mixture of aromatics andparaffins produced by the steps of: a) pyrolyzing and catalyticallyreacting the biomass in a fluid bed reactor, b) quenching the productmixture by admixture with water or a hydrocarbon liquid, c) separatingvapors from the water quench mixture, d) condensing and separating anorganic phase from the vapors, e) separating the organic phase intohigher boiling and lower boiling fractions, f) hydrotreating at least aportion of the lower boiling fraction, and g) recovering renewablegasoline blendstocks and chemicals therefrom. The steps of separatingthe organic phase into higher and lower boiling fractions andhydrotreating (steps e and f) may be reversed, i.e. step f) thehydrotreatment of the condensed materials may be conducted before orafter step e) the separation into higher boiling and lower boilingfractions.

In one embodiment of the invention, step e), separation of the organicphase into higher boiling and lower boiling fractions, is conducted toseparate the materials boiling about 185° C. and higher from thoseboiling below 185° C. After removal of the materials that boil 185° C.and higher, the mixture may comprise at least 25, or at least 35, or atleast 40, or from 25 to 60, or from 35 to 55 volume % toluene, and atleast 15, or at least 20, or at least 25, or from 15 to 40, or from 20to 35 volume % benzene, and at least 5, or at least 8, or at least 10,or from 5 to 20, or from 8 to 15 volume % xylenes, and less than 15, orless than 10, or less than 5, or from 0.01 to 15, or from 2 to 10 volume% the sum of trimethylbenzenes, naphthalene, and other high boilingmaterials, and less than 10, or less than 5, or less than 3, or from 0.5to 10, or from 1 to 5 volume % paraffins, and less than 0.4, or lessthan 0.1 weight %, or less than 100 ppm, or less than 25 ppm, or from0.1 to 4000 ppm, or from 1 to 1000 ppm olefins by weight olefins, andless than 10, or less than 5, or less than 2 ppm, or from 0.1 to 10 ppm,or from 0.2 to 5 ppm by weight sulfur, and less than 10, or less than 5,or less than 2 ppm, or from 0.1 to 10 ppm, or from 0.2 to 5 ppm byweight nitrogen, and less than 1, or less than 0.1, or less than 0.01weight %, or less than 100 ppm, or less than 10 ppm, or less than 1 ppm,or from 0.1 to 10000 ppm, or from 0.2 to 1000 ppm oxygen by weight. Themixture may have a calculated octane rating ((R+M)/2) of at least 100,or at least 103, or at least 105, or from 103 to 111, or from 105 to109. The mixture may have a calculated RVP of less than 5, or less than3, or less than 2 psi.

Other embodiments of the present invention are renewable fuelblendstocks or processing feedstocks that comprise a mixture ofaromatics and paraffins produced by the steps of: pyrolyzing andcatalytically reacting biomass in a fluid bed reactor, quenching theproduct mixture by admixture with water or a hydrocarbon liquid,separating vapors from the water quench mixture, condensing andseparating an organic phase from the vapors, separating the organicphase into a higher boiling and a lower boiling fraction, hydrotreatingat least a portion of the lower boiling fraction, recovering condensableproducts therefrom, and separating the condensed products into afraction boiling below about 85° C. and a fraction boiling above about85° C. The lower boiling fraction may comprise at least 75, or at least85, or at least 90, or from 75 to 99.9, or from 85 to 99 volume %benzene by volume, and less than 20%, or less than 15%, or less than 10,or from 1 to 20, or from 5 to 10 volume % pentanes, hexanes, andheptanes by volume, and less than 20, or less than 15, or less than 10,or from 1 to 20, or from 2 to 15 volume % by volume of the sum oftoluene, xylenes, ethyl benzene, and trimethylbenzenes, and less than0.4%, or less than 0.1 weight %, or less than 100 ppm, or less than 25ppm, or from 1 to 1000 ppm, or from 2 to 25 ppm olefins by weight, andless than 10, or less than 5, or less than 2 ppm, or from 0.01 to 10, orfrom 0.01 to 5 ppm by weight sulfur, and less than 10, or less than 5,or less than 2, or from 0.01 to 10, or from 0.01 to 5 ppm by weightnitrogen, and less than 1%, or less than 0.1%, or less than 0.01 weight%, or less than 100 ppm, or less than 10 ppm, or less than 1 ppm, orfrom 0.01 to 1000 ppm, or from 0.01 to 10 ppm oxygen by weight. Themixture may have a calculated octane rating (R+M/2) of at least 99, orat least 100, or at least 101, or from 99 to 103, or from 101 to 103.The mixture may have a calculated RVP of less than 7, or less than 5, orless than 4 psi. The higher boiling fraction may comprise at least 50%,or at least 60%, or at least 65 volume % toluene, and at least 10, or atleast 15, or at least 20 volume % xylenes and less than 15, or less than10, or less than 5 volume % benzene, and less than 15, or less than 10,or less than 6 volume % C₉ and higher aromatics, and less than 2, orless than 1, or less than 0.5 volume % paraffins, and less than 0.4, orless than 0.1 weight %, or less than 100 ppm, or less than 25 ppmolefins by weight, and less than 10, or less than 5, or less than 2 ppmby weight sulfur, and less than 10, or less than 5, or less than 2 ppmby weight nitrogen, and less than 1, or less than 0.1, or less than 0.01weight %, or less than 100 ppm, or less than 10 ppm, or less than 1 ppmoxygen by weight. The mixture may have a calculated octane rating((R+M)/2) of at least 100, or at least 105, or at least 107, or from 100to 117, or from 105 to 111. The mixture may have a calculated RVP ofless than 3, or less than 2, or less than 1.5 psi. Another embodiment ofthe invention comprises a mixture of the higher boiling fraction withpetroleum derived materials such as gasoline wherein the higher boilingfraction comprises from 0.1 to 10 volume % and gasoline comprises from90 to 99.9 volume % of the mixture. Another embodiment of the inventioncomprises a mixture of the higher boiling fraction with ethanol whereinthe higher boiling fraction comprises from 1 to 25 volume % and ethanolcomprises from 75 to 99 volume % of the mixture.

Another embodiment of the present invention is a renewable fuelblendstock or processing feedstock that comprises a mixture ofhydrocarbons produced by the steps of: pyrolyzing and catalyticallyreacting biomass in a fluid bed reactor, quenching the product mixtureby admixture with water or a hydrocarbon liquid, separating vapors fromthe water quench mixture, condensing and separating an organic phasefrom the vapors, separating the organic phase into higher boiling and alower boiling fractions, hydrotreating at least a portion of the lowerboiling fraction, recovering condensable products therefrom, separatingthe condensed products into a fraction boiling below about 85° C. and afraction boiling about 85° C., and above, and hydrotreating the fractionboiling below about 85° C. The mixture comprises at least 80, or atleast 85, or at least 90, or at least 95, or from 80 to 99 volume %cyclohexane, and less than 1%, or less than 0.1 weight %, or less than100 ppm, or less than 10 ppm, or from 1 ppm to 1% by weight benzene, andless than 10, or less than 7, or less than 5, or from 1 to <10 volume %pentanes, hexanes, and heptanes, and less than 1, or less than 0.1weight %, or less than 100 ppm, or less than 10 ppm, or from 1 ppm to <1weight % by weight the sum of toluene, xylenes, trimethyl benzenes, andnaphthalene, and less than 100 ppm, or less than 10 ppm, or less than 1ppm, or from 0.1 to <100 ppm olefins by weight, and less than 5, or lessthan 2, or less than 1 ppm, or from 0.1 to <5 ppm by weight sulfur, andless than 10, or less than 5, or less than 2 ppm, or from 1 to <10 ppmby weight nitrogen, and less than 1%, or less than 0.1%, or less than0.01 weight %, or less than 100 ppm, or less than 10 ppm, or less than 1ppm, or from 1 ppm to <0.1 weight % oxygen. The mixture may have acalculated octane rating ((R+M)/2) of at least 70, or at least 75, or atleast 80, or from 75 to 80, or from 76 to 77. The mixture may have acalculated RVP of less than 7, or less than 5, or less than 4, or from 2to <7, or from 3 to 5 psi. Another embodiment of the invention comprisesa mixture of the hydrotreated lower boiling fraction with petroleumderived materials. The mixture may be further purified to provide a highpurity chemical feedstock quality cyclohexane that comprises at least95, or at least 99, or at least 99.5% cyclohexane. Another embodiment ofthe invention comprises a mixture of the hydrotreated fraction withpetroleum derived materials such as gasoline wherein the hydrotreatedfraction comprises from 0.1 to 10 volume % and gasoline comprises from90 to 99.9 volume % of the mixture. Another embodiment of the inventioncomprises a mixture of the hydrotreated fraction with ethanol whereinthe hydrotreated fraction comprises from 1 to 25 volume % and ethanolcomprises from 75 to 99 volume % of the mixture %, or at least 99%, orat least 99.5% cyclohexane.

The hydrotreatment of the lower boiling fraction may be conducted bycontacting the liquid with a H₂ containing gas at a pressure from 0.1MPa to 10 MPa (1 to 100 atm), preferably 0.2 to 2 MPa (2 to 20 atm) at atemperature from 40 to 350° C., preferably from 40 to 200° C., in thepresence of a solid catalyst. Solid catalysts useful for thehydrotreating process include Ni, Co, Fe, Cu, Zn, Ag, Pt, Pd, Ru, Rh,Ir, Mo, W, or combinations thereof, deposited on oxide supportsincluding oxides of Al, Si, Ti, Zr, Th, Mg, Ca, or some combination ofthese, either as crystalline solids or as amorphous mixtures. In somecases the catalyst may comprise chlorinated alumina, a zeolitic alumina,active carbon, clays, aluminous cements, rare earth oxides, oralkaline-earth oxides. The hydrotreatment can be carried out in a fixedbed, trickle bed, catalytic distillation reactor, multi-tubular reactor,or fluid bed reactor, with counter- or co-current flow of feed andhydrogen. Suitable conditions and operation of distillation reactors aredescribed in U.S. Pat. No. 8,808,533, and United States PatentPublication 2010/0063334, incorporated herein by reference.

Another embodiment of the present invention is a renewable fuelblendstock that comprises a mixture of aromatics and paraffins producedby the steps of pyrolyzing and catalytically reacting biomass in a fluidbed reactor, quenching the product mixture by admixture with water or ahydrocarbon liquid, separating vapors from the water quench mixture,condensing and separating an organic phase from the vapors, separatingthe organic phase into a higher boiling and a lower boiling fraction,hydrotreating at least a portion of the lower boiling fraction,recovering condensable products therefrom, separating the condensedproducts into a fraction boiling below about 85° C. and a fractionboiling above about 85° C., hydrotreating the fraction boiling belowabout 85° C., and combining the separated higher boiling fraction andthe hydrotreated fraction boiling below about 85° C. The mixture maycomprise from 1 to 99 volume % of the hydrotreated materials boilingbelow 85° C., and from 1 to 99% by volume of the material boiling at orabove 85° C. The mixture comprises at least 10, or at least 20, or atleast 25, or at least 27, or from 10 to 40 volume % cyclohexane, and atleast 30, or at least 35, or at least 40, or at least 45, or from 30 to60 volume % toluene, and at least 5, or at least 10, or at least 14, orfrom 5 to 25 volume % xylenes, and less than 10, or less than 5, or lessthan 3, or from 1 to <10 volume % benzene, and less than 5, or less than3, or less than 2, or from 0.1 to <5 volume % hexanes and pentanes, andless than 1, or less than 7, or less than 5, or from 1 to <10 volume %the sum of trimethylbenzenes and naphthalene, and less than 0.4, or lessthan 0.1 weight %, or less than 100 ppm, or less than 25 ppm, or lessthan 1 ppm, or from 0.1 ppm to <0.4 weight % olefins, and less than 5,or less than 2, or less than 1 ppm, or from 0.1 to <5 ppm by weightsulfur, and less than 10, or less than 5, or less than 2 ppm, or from0.1 to <10 ppm by weight nitrogen, and less than 1, or less than 0.1, orless than 0.01 weight %, or less than 100 ppm, or less than 10 ppm, orless than 1 ppm, or from 0.1 ppm to <1 weight %, or from 0.1 to 100 ppmoxygen by weight. The mixture may have a calculated octane rating((R+M)/2) of at least 95, or at least 97, or at least 100, or from 95 to110, or from 97 to 105. The mixture may have a calculated RVP of lessthan 5, or less than 3, or less than 2, or from 0.1 to <5 psi. Anotherembodiment of the invention comprises the mixture of the above mixturewith petroleum derived materials, or ethanol, or both in a gasolineproduct. Another embodiment of the invention comprises a mixture of thisrenewable mixture with petroleum derived materials such as gasolinewherein the renewable mixture comprises from 0.1 to 10 volume % andgasoline comprises from 90 to 99.9 volume % of the mixture. Anotherembodiment of the invention comprises a mixture of the renewable mixturewith ethanol wherein the renewable mixture comprises from 1 to 25 volume% and ethanol comprises from 75 to 99 volume % of the mixture.

Gasoline is a complex mixture of many hundreds of individual chemicals,made from various blend stocks that are produced in a refinery orproduced elsewhere and blended either at the refinery or at thedistribution terminal (e.g. ethanol splash blending). To meet technical,regulatory, and commercial requirements, the gasoline finished blendmust meet several constraints including limits on vapor pressure,benzene content, sulfur, octane, etc., and minimum volumes to sell intothe consumer market while realizing a profit. Therefore it is possiblethat more than one combination and proportion of various blend stockscan result in a finished gasoline meeting all of the constraints andrequirements. Due to both the importance of and difficulty inidentifying profitable blends meeting specifications, refiners generallyrely on advanced computational tools, primarily Linear or Non-LinearProgramming methods (“LPs”), to accomplish their goals.

In one embodiment, a gasoline blending system can be used to combine apetroleum-derived gasoline with at least a portion of the renewablebiomass derived blendstocks of the inventive process to producerenewable gasoline compositions. The renewable gasoline composition cancomprise petroleum-derived gasoline in an amount of at least 80, or 85,or 90, or 95 volume %, and/or up to 96, or 98, or 99, or 99.5, volume %;or from 80 to 99.5, or from 90 to 98 volume %, and the renewableblendstock fraction in an amount of at least 0.1, or 0.5, or 1, or 5,volume % and/or up to 20, or 15, or 10, or 5, volume %, or from 0.1 to20, or from 1 to 10 volume %. The renewable gasoline compositions mayhave octane ratings ((R+M)/2) of at least 87, or at least 90, or atleast 92, RVP of less than 10, or less than 9, or less than 8, or from 5to 10 psi, sulfur contents of less than 30, or less than 20, or lessthan 10, or from 1 to 30, or from 2 to 20 ppm, aromatics contents ofless than 30, or less than 25 or less than 16 volume %, or at least 5,or at least 10, or at least 15, or from 5 to 30, or from 15 to 25 volume%.

Alternatively, in another embodiment, a gasoline blending system can beused to combine a petroleum derived gasoline with ethanol and at least aportion of the renewable biomass derived blendstocks of the inventiveprocess to produce renewable gasoline compositions. The renewablegasoline composition can comprise petroleum-derived gasoline in anamount of at least 80, or 85, or 90, or 95 volume percent and/or at most96, or 98, or 99, or 99.5, volume percent; or from 80 to 99.5, or from90 to 98 volume %, ethanol in an amount of at least 1, or at least 5, orat least 10, or up to 25, or up to 20, or up to 15 or up to 10 volumepercent, or from 1 to 20, or from 5 to 15 volume %, and the renewableblendstock fraction in an amount of at least 0.1, or 0.5, or 1, or 5, or8, volume % or up to 20, or 15, or 10, or 5, or from 0.1 to 20, or from1 to 10 volume %. The renewable gasoline compositions may have octaneratings ((R+M)/2) of at least 87, or at least 90, or at least 92, RVP ofless than 10, or less than 9, or less than 8, or from 5 to <10 psi,sulfur contents of less than 30, or less than 20, or less than 10, orfrom 1 to <30, or from 2 to 20 ppm, aromatics contents of less than 30,or less than 25 or less than 16 volume percent, or at least 5, or atleast 10, or at least 15, or from 5 to 30, or from 15 to 25 volume %.

Alternatively, in another embodiment, a gasoline blending system can beused to combine ethanol and at least a portion of the renewable biomassderived blendstocks of the inventive process to produce essentially 100%renewable gasoline compositions. The renewable gasoline composition cancomprise ethanol in an amount of at least 60, or 70, or 80, or 85,volume percent and/or up to 90, or 95, or 99, volume percent; or from 70to 99, or from 80 to 90 volume %, and the renewable blendstock fractionin an amount of at least 1, or at least 5, or at least 10, or at least15, or up to 40, or up to 30, or up to 20, or up to 15 volume %, or from1 to 40, or from 5 to 15 volume %. The renewable gasoline compositionsmay have octane ratings ((R+M)/2) of at least 87, or at least 90, or atleast 92, or at least 100, RVP of less than 10, or less than 9, or lessthan 8, or less than 6, or from 3 to 9 psi, sulfur contents of less than30, or less than 20, or less than 15, or from 1 to <30, or from 2 to 20ppm, aromatics contents of less than 30, or less than 25 or less than 16volume %, or at least 5, or at least 10, or at least 15, or from 5 to<30, or from 10 to 25 volume %.

The following Examples demonstrate the present invention and itscapability for use. The invention is capable of other and differentembodiments, and its several details are capable of modifications invarious apparent respects, without departing from the spirit and scopeof the invention. Accordingly, the Examples are to be regarded asillustrative in nature and not as restrictive. All percentages are byweight unless otherwise indicated.

Example 1

An Aspen™ model was prepared to evaluate the Bio-TCat™ process andproduct upgrading and separation processes in FIGS. 1, 2, 3, and 4. Inthe model a mixture of materials simulating the raw liquid productcondensed from the Bio-TCat™ process was hydrotreated under mildconditions to produce a product stream that has reduced concentrationsof sulfur, nitrogen, olefins, dienes, oxygenates, and other impurities.The whole hydrotreated stream may be identified as the “C₅ ⁺ LiquidProduct” and a fraction from which the higher boiling materials havebeen separated by distillation may be identified as a “C₅-C₉ ProductCut,” identified as stream 1 in FIGS. 1, 2, 3, and 4. The C₅ ⁺ LiquidProduct comprises all molecules with carbon numbers of 5 or more,including molecules that boil outside of the gasoline range. The C₅-C₉Product Cut boils in the gasoline range and is a partially refinedproduct contained within the C₅ ⁺ product. It is obtained bydistillation of the C₅ ⁺ product. After mild hydrotreating, modelcalculations show that the concentration of heteroatom species in theC₅-C₉ Product Cut is less than 1 ppm of sulfur, less than 1 ppm ofnitrogen, and olefins, dienes, and styrenes contents are also reduced toless than 100 ppm. The C₅-C₉ Bio-TCat™ product after mild hydrotreatingis called “AnelloMate Full Range Product”. The compositions of thevarious fractions were calculated using the model and are collected inTable 3 (all values are ppm by weight).

TABLE 3 (Composition of Bio-TCat ™ Product (C₅ ⁺ Liquid Product) andAnelloMate Full Range (C₅-C₉ Product Cut) products before and after MildHydrotreating (HDT) Composition of Liquid Composition of Liquid ProductBefore HDT Product After HDT Heteroatoms & C5-C9 C5-C9 Unsaturates C5+Liquid Product C5+ Liquid Product ppmw Product Cut Product Cut Oxygen7,959 3,479 <1 <1 Sulfur 59 74 <1 <1 Nitrogen 335 434 <1 <1 C5+ Olefins5,958 8,994 <100 <100 C5+ Dienes 0 0 <100 <100 Styrenes 4,727 6,134 <100<100

The results in Table 3 show that mild hydrotreating of the whole liquidproduct of the Bio-TCat™ process and the C₅-C₉ product cut separatedtherefrom results in a product stream that has sulfur, nitrogen, andoxygen concentrations that are below detection limits, i.e. less than 1ppm, and that the concentration of olefins and dienes is below 100 ppmindicating that the stream is a valuable feed for gasoline blendstocksor chemicals production.

Example 2

A computational model of the inventive process as depicted in FIG. 1 wasdeveloped in Aspen™. The Benfree™ benzene hydrogenation processconversions and selectivities were obtained from commercial sources. InTable 4 are collected the compositions of the various product streams ascalculated in the computational model. The lower section of Table 4includes the fuel-relevant physical properties of the various streamsincluding density, the volume percent of each stream relative to thestarting Bio-TCat™ full-range product, and calculated octane numbers andvapor pressures.

The volume percentages after separation, hydrogenation, andrecombination add up to a number above 100%. This phenomenon iswell-known in the oil refining industry where it is referred to as“volume swell”. While mass is conserved in any system, volume is notnecessarily conserved. Volume swell occurs because of density changesthat occur when molecules are converted from one type to another. Inthis case, the volume swell is attributed to conversion of benzene tocyclohexane, where the densities of the pure compounds are 885 and 785kg/m³, respectively (reference NIST Standard Reference Database 69: NISTChemistry WebBook).

Based on the chemical compositions, the octane numbers of the mixturesobtained from the process model have been estimated using the chemicalcompositions in Table 3 with the octane number blending model of Jaffeet al (Ind. Eng. Chem. Res. 2006, 45, 337-345).

Based on the chemical compositions obtained from the process model theReid Vapor Pressures of the product mixtures are presented in Table 4.The calculation was performed using Equation 2, above, wherein vi is thevolume fraction of each stream making up the final gasoline blend, RVPiis the blending RVP of each stream, and RVPmix is the RVP of theresulting final blend. The calculated RVP of each AnelloMate streambased on the RVP of each identifiable chemical compound is presented inTable 4 (percentages in volume).

TABLE 4 (Compositions and Properties of Product Streams of the Processin FIG. 1) Streams 6 5 5 + 6 1 4 AnelloMate AnelloMate AnelloMateAnelloMate AnelloMate Light Naphtha C7-C9 Heavy Combined Full-RangeC6-Splitter After Benzene Naphtha from Cyclohexane + Compound, vol %Product Light Naphtha Saturation C6-Splitter C7-C9 i-pentane 0.1% 0.2%0.1% 0.0% 0.0% n-pentane 0.3% 0.8% 0.5% 0.0% 0.2% hexanes & hexenes 0.6%1.7% 1.4% 0.0% 0.5% benzene 34.9% 97.0% 0.0% 1.9% 1.2% cyclohexane 0.0%0.0% 97.8% 0.0% 36.3% heptanes & heptenes 0.2% 0.3% 0.3% 0.2% 0.2%methyl cyclohexane 0.0% 0.0% 0.0% 0.0% 0.0% toluene 45.5% 0.0% 0.0%69.6% 43.8% octanes & octenes 0.2% 0.0% 0.0% 0.2% 0.1% ethyl benzene0.8% 0.0% 0.0% 1.2% 0.7% o-xylene 2.9% 0.0% 0.0% 4.4% 2.8% m-xylene 6.7%0.0% 0.0% 10.3% 6.5% p-xylene 4.4% 0.0% 0.0% 6.7% 4.2% nonane & nonenes0.1% 0.0% 0.0% 0.1% 0.1% C9 aromatics 2.1% 0.0% 0.0% 3.2% 2.0% C10+aromatics 1.4% 0.0% 0.0% 2.2% 1.4% Total 100.0% 100.0% 100.0% 100.0%100.0% Density @ 15 C/4, kg/m3 873 878 781 871 837 Calculated RON 111102 82 116 108 Calculated MON 104 104 77 103 97 Calculated (R + M/2) 107103 80 110 102 Calculated RVP, psia 1.9 3.2 3.1 1.0 1.9 Total Aromatics98.6% 97.0% 0.0% 99.5% 62.6%

The data in Table 4 show that valuable gasoline blending stocks can beprepared from the products of the Bio TCat™ process according to thescheme depicted in FIG. 1. The data in Table 4 show that blendstocksprepared by the inventive process including pyrolyzing and catalyticallyreacting the biomass in a fluid bed reactor, quenching the productmixture by admixture with water or a hydrocarbon liquid, separatingvapors from the water quench mixture, condensing and separating anorganic phase from the vapors, hydrotreating at least a portion of thecondensed organic phase have physical properties that can be useful forblending with gasoline to provide fuel mixtures that meet regulatorystandards with respect to octane, benzene content, sulfur content, orRVP.

Example 3

A gasoline blending Linear Programming model was written in Excel-Solverto describe a generic refinery operation and the various blend stocksthat are produced within it using literature sources for refinery streamyields and blending properties. This model was then used to createfinished gasoline blends containing targeted percentages of renewablecontent using ethanol and AnelloMate products, either alone or ascombinations of each, blended into a gasoline base blend (“BOB” orblendstock for oxygenate blending”). In the LP model, the refinery isassumed to have a source of n-butane for RVP control, a naphthahydrotreater to reduce sulfur, a C₅/C₆ paraffin isomerization unit, alight naphtha benzene saturation unit, a fluid catalytic cracker (FCC),a FCC naphtha post-hydrotreater unit, a sulfuric acid alkylation unit,and a naphtha reformer. Operation of these units is constrained bythroughput and mass balance. The current target of the EPA is thatrenewables should contribute at least 10 volume percent to the pool. Forethanol, there is also a regulated minimum level of 5.9 volume percentin some states. This represents a further constraint on blendingcalculations.

The LP model was run to make variable amounts of a finished gasolinehaving properties that meet regulatory, technical, and commercialrequirements. Specific specification limits included;

-   -   Benzene content less than 0.62 volume % (U.S. pool average        requirement)    -   Sulfur content less than 10 ppm (U.S. 2017 requirement)    -   RVP of less than 7.8 (Summer season requirement)    -   Total aromatics less than 25 volume % (CARB gasoline        requirement)    -   87 (R+M)/2 octane (regular grade gasoline)

Table 5 shows the properties of the renewable fuel component used in theLinear Programming model to make the finished gasoline. Table 6 showsseveral blend compositions and blend properties calculated with theLinear Programming model for various BOB/Ethanol/AnelloMate mixtures.For ethanol-only blending, the 1 psi waiver allowance was not used.

TABLE 5 (Gasoline blending properties for AnelloMate products, ethanol,and gasoline specifications) AnelloMate AnelloMate AnelloMate SplashRefinery Full-Range Hydro- C7-C9 Heavy Blended Gasoline BOB C5-C9Treated C6 Naphtha Ethanol Renewable Content, vol %   0%  100%  100% 100%  100% Benzene, vol % 0.41% 34.86%  0.00% 1.92% 0.00% Sulfur, ppm7.0 0.5 0.0 0.5 20 RVP, psi 6.0 0.8 1.5 0.4 33.9 RVP Index 9.4 0.8 1.70.3 81.7 Total Olefins, vol % 13.4%  0.0%  0.0%  0.0%  0.0% TotalAromatics, vol % 24.3% 98.6%  0.0% 99.5%  0.0% Octane (R + M)/2 85.4107.4 79.7 109.6 113

TABLE 6 (Fuel Blend Compositions and Properties for Ethanol andAnelloMate with Gasoline) 100% 87 Octane Renewable Gasoline 90 OctaneGasoline with Gasoline with 85% AnelloMate with Ethanol Target 10% andAnelloMate and 15% Blended Fuel Specification Ethanol Ethanol andEthanol AnelloMate Blend Stocks, Volume % Refinery Gasoline, BOB —   90%  90% 76.2%  0.0% AnelloMate Hydrotreated C6 — —  1.3%  2.7%  4.6%AnelloMate C7-C9 Heavy — —  2.8%  6.1% 10.4% Naphtha Splash BlendedEthanol — 10%  5.9% 15.0% 85.0% Blend Parameters Renewable Content, vol% 10.0% 10.0% 10.0% 23.8% 100.0% Benzene Maximum, vol % 0.62% 0.37%0.42% 0.43% 0.20% Sulfur Maximum, ppm 10 8.3 7.5 8.4 17.1 RVP Maximum,psi 7.8 7.8 7.8 8.5 5.6 Total Olefins, vol % — 12.1% 12.1% 10.2%  0.0%Total Aromatics Maximum, vol %   25% 21.8% 24.7% 23.0% 10.4% OctaneMinimum (R + M)/2 87 87.5 87.6 90.3 110.7 Energy Content Versus — 96.8%98.1% 95.2% 72.8% Gasoline, %

The results in Table 6 show that gasoline blendstocks prepared by thesteps of pyrolyzing and catalytically reacting the biomass in a fluidbed reactor, quenching the product mixture by admixture with water or ahydrocarbon liquid, separating vapors from the water quench mixture,condensing and separating an organic phase from the vapors, andhydrotreating at least a portion of the condensed products, can beuseful for blending with gasoline to provide fuel mixtures that meetregulatory standards and in some cases have higher octane, lowerbenzene, lower sulfur, lower RVP, or lower RVP Index, or somecombination of these features compared to 10% ethanol in gasoline fuel.

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with this invention and for all jurisdictions in which suchincorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and may be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimshereof be limited to the examples and descriptions set forth herein butrather that the claims be construed as encompassing all the features ofpatentable novelty which reside in the present invention, including allfeatures which would be treated as equivalents thereof by those skilledin the art to which the invention pertains.

What is claimed is:
 1. A fuel blendstock comprising from 25 to 60 volume% toluene, from 15 to 40 volume % benzene, from 5 to 20 volume %xylenes, from 0.01 to 15 volume % C₉ ⁺ aromatics, from 0.5 to 10 volume% paraffins, less than 0.4 weight % olefins, less than 10 ppm by weightsulfur, less than 10 ppm by weight nitrogen, and less than 1 weight %oxygen, said blendstock having a calculated octane rating ((R+M)/2) ofat least 100, and a calculated RVP of less than 5 psia.
 2. A mixturecomprising from 90 to 99.9 volume % gasoline and from 0.1 to 10 volume %blendstock of claim
 1. 3. A mixture comprising from 75 to 99 volume %ethanol and from 1 to 25 volume % blendstock of claim
 1. 4. A fuelblendstock comprising 75 to 99.9 volume % benzene, from 1 to 20 volume %total pentanes and hexanes, from 1 to 20 volume % total toluene,xylenes, ethylbenzene and trimethylbenzenes, less than 0.4 weight %olefins, less than 10 ppm by weight sulfur, less than 10 ppm by weightnitrogen, and less than 1 weight % oxygen, said blendstock having acalculated octane rating ((R+M)/2) of at least 99, and a calculated RVPof less than 7 psia.
 5. A mixture comprising from 90 to 99.9 volume %gasoline and from 0.1 to 10 volume % blendstock of claim
 4. 6. A mixturecomprising from 75 to 99 volume % ethanol and from 1 to 25 volume %blendstock of claim
 4. 7. A fuel blendstock comprising 50 to 99 volume %toluene, 10 to 40 volume % xylenes, from 0.1 to 15 volume % benzene,from 1 to 15 volume % C₉ ⁺ aromatics, from 0.01 to 2 volume % paraffins,less than 0.4 weight % olefins, less than 10 ppm by weight sulfur, lessthan 10 ppm by weight nitrogen, and less than 1 weight % oxygen, saidblendstock having a calculated octane rating ((R+M)/2) of at least 100,and a calculated RVP of less than 3 psia.
 8. A mixture comprising from90 to 99.9 volume % gasoline and from 0.1 to 10 volume % blendstock ofclaim
 7. 9. A mixture comprising from 75 to 99 volume % ethanol and from1 to 25 volume % blendstock of claim
 7. 10. A fuel blendstock orchemical stock comprising from 1 ppm to 1 weight % benzene, from 1 to 10volume % total pentanes and hexanes, from 1 ppm to 1% by weight totaltoluene, xylenes, trimethylbenzenes and naphthalene, from 80 to 99volume % cyclohexanes selected from the group consisting of cyclohexane,methyl-cyclohexane, dimethyl-cyclohexane, ethyl-cyclohexane,methyl-ethyl-cyclohexane, propyl-cyclohexanes, and combinations thereof,less than 0.4 weight % olefins, less than 10 ppm by weight sulfur, lessthan 10 ppm by weight nitrogen, and less than 1 weight % oxygen, saidblendstock or chemical stock having a calculated octane rating ((R+M)/2)of at least 75, and a calculated RVP of less than 7 psia.
 11. A mixturecomprising from 75 to 99 volume % ethanol and from 1 to 25 volume %blendstock of claim
 10. 12. A fuel blendstock comprising from 30 to 60volume % toluene, from 1 to 10 volume % benzene, from 5 to 25 volume %xylenes, from 0.1 to 5 volume % total pentanes and hexanes, from 1 to 10volume % total trimethylbenzenes and naphthalene, from 10 to 40 volume %cyclohexanes selected from the group consisting of cyclohexane,methyl-cyclohexane, dimethyl-cyclohexane, ethyl-cyclohexane,methyl-ethyl-cyclohexane, propyl-cyclohexanes, and combinations thereof,less than 0.4 weight % olefins, less than 10 ppm by weight sulfur, lessthan 10 ppm by weight nitrogen, and less than 1 weight % oxygen, saidblendstock having a calculated octane rating ((R+M)/2) of at least 95,and a calculated RVP of less than 5 psia.
 13. A mixture comprising from90 to 99.9 volume % gasoline and from 0.1 to 10 volume % blendstock ofclaim
 12. 14. A mixture comprising from 75 to 99 volume % ethanol andfrom 1 to 25 volume % blendstock of claim
 12. 15. A mixture comprisingfrom 80 to 99.5 volume % gasoline and from 0.5 to 20 volume % blendstockof claim
 12. 16. A mixture comprising from 80 to 99.5 volume % gasoline,from 1 to 20 volume % ethanol, and from 0.1 to 20 volume % blendstock ofclaim
 12. 17. A mixture comprising from 1 to 99 volume % blendstock ofclaim 10 and from 1 to 99 volume % blendstock of claim
 12. 18. A mixturecomprising from 80 to 99 volume % gasoline and from 1 to 20 volume %mixture of claim
 17. 19. A mixture comprising from 75 to 99 volume %ethanol and from 1 to 25 volume % mixture of claim
 17. 20. A fuelblendstock comprising 50 to 99 volume % total cyclohexane,methyl-cyclohexane, dimethyl-cyclohexane, ethyl-cyclohexane,methyl-ethyl-cyclohexane, and propyl-cyclohexanes, less than 15 volume %benzene, from 0.01 to 2 volume % paraffins, less than 0.4 weight %olefins, less than 10 ppm by weight sulfur, less than 10 ppm by weightnitrogen, and less than 1 weight % oxygen, said blendstock having acalculated octane rating ((R+M)/2) of at least 70, and a calculated RVPof less than 7 psia.
 21. A mixture comprising from 90 to 99.9 volume %gasoline and from 0.1 to 10 volume % blendstock of claim
 10. 22. Amixture comprising from 50 to 99 volume % ethanol and from 1 to 50volume % blendstock of claim
 10. 23. A mixture comprising from 50 to 99volume % diesel fuel and from 1 to 50 volume % of the blendstock ofclaim
 10. 24. A mixture comprising from 50 to 99 volume % jet fuel andfrom 1 to 50 volume % of the blendstock of claim 10.